CN100454148C - Particle dispersion for electrostatic image-developing toners, electrostatic image-developing toner, and method for producing the same - Google Patents

Abstract

The invention provides a particle dispersion for an electrostatic image-developing toner containing either polycondensation resin particles, which are prepared by polycondensation of polycondensable monomers in an aqueous medium, or condensation compound particles, which are prepared by dehydration condensation of a condensable compound in an aqueous medium. The particles have a median diameter of approximately 0.05 to 2.0 mum. A dispersion containing the polycondensation resin particles is produced by dispersing resin particles, aggregating the resin particles, and coalescing the aggregated particles by heating. A dispersion containing the condensation compound particles is produced by dispersing resin particles, dispersing condensation compound particles, aggregating the resin particles and the condensation compound particles in a mixture dispersion, obtained by mixing the dispersion of the resin particles and the dispersion of the condensation compound particles, and coalescing the aggregated particles by heating.

Description

The particle dispersion, electrostatic image-developing toner and the manufacture method thereof that are used for electrostatic image-developing toner

The cross-reference of related application

It is right of priority that the application requires with Japanese patent application 2004-363264 and 2004-363265 according to 35 USC 119, its disclosed content with referring to form be incorporated herein.

Technical field

The present invention relates to developer to the employed electrostatic image-developing toner that develops by electrofax, static and the formed electrostatic latent image of other writing-method, its manufacture method and as the resin particle of raw material or the dispersion liquid of condensation compound particle.

Background technology

By electrostatic image the method for information visualization is applied in a lot of fields such as electronic camera technology etc. at present.In this electronic camera technology, come displays image information by following steps: by electrostatic charging or exposure on photoreceptor, form electrostatic image, developing with the developer that contains toner forms thereon electrostatic latent image and the image that developed of transfer printing and photographic fixing.Contain the tow-component developer of toner and carrier and only use single component developer of a kind of magnetic color tuner or nonmagnetic toner all known as the employed developer of this system.This toner is made in kneading-grinding technics usually, and described technology comprises with thermoplastic resin and pigment, charge control agent and such as releasing agents such as paraffin carries out fusion-mixing, grinds and classification with the potpourri cooling and to the resin of cooling.If desired, the inorganic or organic fine particles adjuvant as the toner-particle surface can be added in the toner to improve liquidity and cleanability sometimes.

Recently, use the duplicating machine and the printer of color electronography method and to comprise the multi-function processor and the facsimile recorder of this equipment universal day by day.Owing to usually be difficult to use,, on fixing roller, applied a large amount of oil and discharged promoting therefore in order in the color reproduction image process, to obtain the transparency of preferable image glossiness and good overhead projector (OHP) image such as releasing agents such as waxes.As a result, be difficult to prevent to comprise the soapy feeling of the duplicating image on the OHP paper, and be difficult to for example on duplicating image, add extra literal or image with pen.In addition, You use can cause the glossiness inequality of image usually.Owing to can damage the transparency of gained OHP image, therefore be difficult to use be generally used for common black and white copying such as waxes such as tygon, polypropylene or paraffin.

When using traditional kneading-grinding technics to make toner, be not only and cause such as problems such as transparency deteriorates, and owing to be difficult to the sustained release agent in the lip-deep surface of the toner-particle amount of exposing, therefore when with toner during, can produce mobile rapid deterioration and problem such as plated film on developing machine, photoreceptor etc., occur as developer.

For thoroughly overcoming these problems, proposed to make the method for toner by polymerization, particularly, described method comprises: disperse to contain the oil phase of the monomer of resin base material and colorant and toner is made in the direct polymerization of monomer at aqueous phase, form the inner toner that is encapsulated with wax, control its amount of exposing from the teeth outwards thus.

In addition, open clear JP-A-63-282752 and the special method that has proposed to make by the emulsion polymerization aggregation method toner among the flat 6-250439 of opening is used as systematically controlling the shape of toner and the another kind of means of surface structure the spy.These teach literatures make the common processes of toner, described technology comprises: by manufacturing particulate resin dispersions such as emulsion polymerizations, manufacturing contains the colorant dispersion that is dispersed in the colorant in the solvent, particulate resin dispersion and colorant dispersion is mixed, form and come corresponding to the aggregation of the particle diameter of toner-particle and by heating that fusion-this aggregation condenses.

These manufacture processes not only allow to seal wax in toner-particle inside, and are easy to reduce the particle diameter of toner, and can duplicate more high-resolution picture rich in detail.

As mentioned above, for the performance that high-quality image is provided in electrophotographic processes and under various mechanical stresses, stablizes toner, then the kind and the quantity of employed pigment of optimization and releasing agent, prevent releasing agent exposing on particle surface, do not use photographic fixing oil to improve the glossiness of print image and control heat stained etc. by optimization resin property and release performance to be very important.

On the other hand, consider minimizing of energy consumption, need low temperature image fixing method.Particularly, in recent years, there is demand, for example, removes use external cutting off electric power supply thorough power-economizing method.As a result, this fixation facility should have the function that the temperature of making rises to operating temperature rapidly.For this purpose, need the thermal capacitance of fixation facility as far as possible little.Yet in this case, the temperature fluctuation of fixation facility is usually than big in the conventional situation.For example, become bigger, transmit the temperature that causes by paper and descend and also become big in the back toning temperature that begins to power.And if constantly added the width paper littler than fixation facility, then paper transmission district will increase with the temperature difference that non-paper transmits the district.Particularly, when using above-mentioned functions, duplicating machine and printer at a high speed do not have enough big electric capacity usually, caused above-mentioned phenomenon usually.Thereby, to so-called wide-there is strong demand in the electrofax tinter of photographic fixing-scope, the photographic fixing and also can not cause stained up to high temperature range at low temperatures of this toner.

Known use crystal type condensation resin or crystal type condensation compound are effectively to the fixing temperature that reduces toner, and described crystal type condensation resin or crystal type condensation compound have shown sharper keen melting property as the adhesive resin that is used for toner with respect to temperature.Yet,, thereby can't use usually owing to the crystal type resin more is difficult to grind by fusion-kneading polishing.

The manufacturing of the polymerization of condensation resin and crystal type condensation compound also requires following condition usually: for example high temperature more than 200 ℃, more powerful stirring, highly decompression and 10 hours or longer reaction time, thereby consumed big energy.In addition, also need huge equipment investment to guarantee the permanance of consersion unit.

When making toner by above-mentioned emulsion polymerization aggregation method, produce crystal type condensation resin or crystal type condensation compound by polymerization after, can be converted into the latex condition by emulsification in aqueous medium above-mentioned resin or compound, itself and pigment, wax etc. are condensed, and fusion-resulting aggregation condenses.

Yet, the emulsification of condensation resin or crystal type condensation compound needs the method for the extremely low and high energy consumption of service efficiency, such as, under high shear stress,, or in aqueous medium, be dispersed in the low viscosity solution that is dissolved with resin or compound in the solvent and remove the method for desolvating subsequently at the emulsification method that surpasses under 100 ℃ to 150 ℃ the temperature.

Owing to be difficult to avoid the hydrolysis problem in the emulsion process of aqueous medium, thereby in the material design, also can produce uncertain factor inevitably.

Although these problems clearly when using the crystal type resin, same problem not only occurs when using the crystal type resin, but also can occur when using the non-crystalline type resin.

Having report to point out to it is believed that in aqueous medium is the polycondensation reaction (United States Patent (USP) 4355154) of very difficult polyester.Also relevant for the report of in aqueous medium, in the presence of catalyzer, carrying out the polycondensation reaction of polyester (United States Patent (USP) 4355154) with sulfonic acid group.

Summary of the invention

As mentioned above, in the classical production process of toner, the crystal type condensation resin that in aqueous medium, will obtain by polyreaction or by the synthetic crystal type condensation compound emulsification that obtains.Yet, if possible as above report described resin particle or the condensation compound in aqueous medium, made, the process of emulsifying resins or condensation compound particle is optional in aqueous medium.Therefore this situation is favourable.

Yet in the report that exemplifies in the above, resin particle is with the state emulsification of rather unstable and is dispersed in the aqueous medium.Therefore, make toner by this dispersion liquid and can cause, thereby cause deterioration of image quality such as problems such as toner particle diameter and distribution variation thereof.Therefore, the toner that can't have desired characteristics by this method manufacturing at present.In addition, though will by the resulting crystal type condensation resin of polyreaction or by the synthetic crystalline compound that obtains in aqueous medium during emulsification, resin particle also is with the state emulsification of rather unstable and is dispersed in the aqueous medium.From the viewpoint of recent technology, need improve above-mentioned condition.

Consider above-mentioned condition, the present invention is intended to solve over the problems referred to above that exist and realizes following purpose.Promptly, the invention provides and contain with the low energy consumption stable emulsion and be dispersed in the particulate resin dispersion that is used for electrostatic image-developing toner of the resin particle in the aqueous medium, and contain with the low energy consumption stable emulsion and be dispersed in the condensation compound particle dispersion that is used for electrostatic image-developing toner of the condensation compound particle in the aqueous medium.The present invention also provides the manufacture method of electrostatic image-developing toner, described method can fully satisfy the electrostatic image-developing toner of required toner characteristic by using at least a manufacturing the in these dispersion liquids, and the electrostatic image-developing toner that obtains thus is provided.

The present invention considers above-mentioned situation and makes.Promptly, the invention provides the particulate resin dispersion of the electrostatic image-developing toner that comprises the condensation resin particle, but wherein said condensation resin particle prepares by polycondensation polycondensation monomer in aqueous medium, and has and be about 0.05 micron～2.0 microns median particle diameter.

In addition, the invention provides the condensation compound particle dispersion of the electrostatic image-developing toner that comprises condensation compound, but wherein said condensation compound particle prepares by the compound of dehydrating condensation condensation in aqueous medium, and has and be about 0.05 micron～2.0 microns median particle diameter.

In one embodiment, condensation resin particle or condensation compound particle are that crystal type and its crystalline melting point are about 50 ℃～120 ℃.

In another embodiment, but but polycondensation monomer or condensation compound comprise polybasic carboxylic acid and polyvalent alcohol at least.

In another embodiment, in the presence of as the acid with surfactant properties of catalyzer, but but polycondensation monomer generation polycondensation or condensation compound generation dehydrating condensation.

In another embodiment, in the presence of as the catalyzer that contains rare earth metal of catalyzer or hydrolytic enzyme, but but polycondensation monomer generation polycondensation or condensation compound generation dehydrating condensation.

In addition, the invention provides the manufacture method of electrostatic image-developing toner, described method comprises: but the polycondensation polycondensation monomer disperses condensation resin to obtain the condensation resin particle dispersion in aqueous medium to obtain the condensation resin particle in aqueous medium; Resin particle in the gathering particulate resin dispersion is so that obtain aggregated particle; The particle of having assembled by heat-setting.

In addition, the invention provides the manufacture method of electrostatic image-developing toner, described method comprises: dispersion resin is to obtain particulate resin dispersion in aqueous medium; In aqueous medium, disperse condensation compound to obtain the condensation compound particle dispersion; Particulate resin dispersion is mixed with the condensation compound particle dispersion to obtain mixed dispersion liquid, and resin particle in the aggregated mixed dispersion liquid and condensation compound particle are to obtain aggregated particle; With, the particle of having assembled by heat-setting.

In addition, the invention provides by the prepared electrostatic image-developing toner of the manufacture method of any one electrostatic image-developing toner.

Embodiment

Below, with the present invention is described in detail.

The dispersion liquid of electrostatic image-developing toner

But the condensation resin particle that is obtained by the direct polycondensation of polycondensation monomer in aqueous medium by preparation can obtain the particulate resin dispersion (hereinafter referred is a particulate resin dispersion of the present invention) that is used for electrostatic image-developing toner of the present invention.In addition, but can obtain the condensation compound particle dispersion (hereinafter referred is a condensation compound particle dispersion of the present invention) that is used for electrostatic image-developing toner of the present invention by the condensation compound particle that obtains by the direct condensation of condensation compound in aqueous medium of preparation.In described dispersion liquid, to be about 0.05 micron～2.0 microns median particle diameter with condensation resin particle and the emulsification of condensation compound particle and be dispersed in the aqueous medium.

Because condensation resin/condensation compound particle is direct polycondensation in aqueous medium by this way, therefore be about 0.05 micron～2.0 microns median particle diameter so that condensation resin/condensation compound particle has, can make condensation resin/condensation compound particle in these dispersion liquids of the present invention with low energy consumption.In addition, each condensation resin/condensation compound particle these dispersion liquids separated from one another in aqueous medium wherein, for up to be used to produce toner to utilize coagulator to start the condense prolonging period of operation of polycondensation be stable.Only the mode with highly control has formed aggregated particle after aggregation operator.Therefore, the use of dispersion liquid of the present invention has caused the control more favourable to the homogeneity of the The Nomenclature Composition and Structure of Complexes of the size distribution of toner and toner-particle, thereby the toner with satisfied toner characteristic is provided.

The median particle diameter (mean diameter) of condensation resin/condensation compound particle is about 0.05 micron～2.0 microns, is preferably 0.1 micron～1.5 microns, more preferably 0.1 micron～1.0 microns.As mentioned above, the condensation resin/condensation compound particle with above-mentioned median particle size range is dispersed in the aqueous medium under steady state (SS).Comprise particle diameter and can cause in the manufacture process of toner less than the dispersion liquid of the particle of median particle diameter excessively that the generation frequency of deterioration, the free resin particle of condensation efficiency when making particle increases, the problems such as increase of system viscosity, make the particle diameter that is difficult to the control toner.On the other hand, comprising particle diameter excessively can be because because of the coarse grained expansion that is easy to generate the size distribution that causes and free condensation compound particle and such as the increase of the generation frequency of releasing agent particles such as wax greater than the dispersion liquid of the particle of median particle diameter, thereby causes such as occurring peeling off in the photographic fixing step or discharging problem such as stained temperature reduction.

The median particle diameter of condensation resin/condensation compound particle can be for example by using laser diffraction particle size analyzer (trade name: LA-920, Horiba Ltd. produces) to measure.

In addition, in dispersion liquid of the present invention, ultra-fine and super coarse grained content is preferably less in condensation resin/condensation compound particle.Promptly, general assembly (TW) with respect to condensation resin/condensation compound particle, median particle diameter is about 0.03 micron or weight ratio littler or that be about 5.0 microns or bigger condensation resin/condensation compound particle and is preferably about 10% or littler, more preferably about 5% or littler in the dispersion liquid.This ratio can be by drawing integration frequencies with respect to the particle diameter of being measured by laser diffraction size distribution analyser, and the integration frequencies of measuring 0.03 micron or littler or 5.0 microns or bigger particle is calculated.

Hereinafter will the manufacture method of dispersion liquid of the present invention be described.For making dispersion liquid of the present invention, at first, but but with polycondensation monomer or condensation compound, the raw material of required particle is for example by mechanical shear stress or ultrasonic emulsification and be dispersed in the aqueous medium.Can will be added in the aqueous medium if desired simultaneously such as adjuvants such as catalyzer (condensation catalyst/polycondensation catalyst) and surfactants.But but the solution that for example obtains thus by heating then carries out the polycondensation reaction of polycondensation monomer or the dehydration condensation of condensation compound.

But but the dehydration condensation of the polycondensation reaction of polycondensation monomer and condensation compound all is to be accompanied by the reaction of dehydration thereby not carry out in aqueous medium in principle.Yet, for example, if but but polycondensation monomer or condensation compound in aqueous medium with the surfactant emulsification that can in aqueous medium, form micella because monomer enters in the microcosmic hydrophobic environment of micella, therefore dehydration can take place.Discharging micella by water that will be generated goes forward side by side and can carry out polycondensation reaction or condensation reaction in the water-based medium.In this mode, can obtain emulsification and be dispersed in condensation resin in the aqueous medium or the dispersion liquid of condensation compound particle with low energy consumption.

The median particle diameter of the condensation resin that is used for obtaining thus/condensation compound particle is controlled in the above-mentioned scope and the preference of method that reduces to have the ratio of the condensation resin/condensation compound particle that is greater than or less than median particle diameter comprises following method.

1) directly condensation resin/condensation compound particle is not added in the aqueous medium, but at first mixes and fusion with other one or more adjuvants (its example comprises catalyzer and surfactant).Then the gained oily solution is added in the aqueous medium, makes emulsifying mixture and dispersion by stirring (as the use homogenizer) and stirring for the second time (as using ultrasound wave) for the first time.

2) but one or more adjuvants of polymerisable monomer/condensation compound and other (its example comprises catalyzer and surfactant) are mixed and fusion; The solution that stirring obtains thus also carries out thick emulsification (as using homogenizer) and carries out meticulousr emulsification (as using Yoshida Kikai Co., the nanomizer that Ltd makes) then in being heated to for example about 100 ℃ aqueous medium.

3) but one or more adjuvants of polymerisable monomer/condensation compound and other (its example comprises catalyzer and surfactant) are mixed and fusion; Adding a spot of solvent (as ethyl acetate etc.) afterwards, potpourri is being stirred in aqueous medium and meticulousr emulsification (as use Yoshida Kikai Co., the nanomizer that Ltd provides) is carried out in thick emulsification (as using homogenizer) then; Then, when stirring the mixture and being heated to about 60 ℃, remove and desolvate.

4) but one or more adjuvants of polymerisable monomer/condensation compound and other (its example comprises catalyzer and surfactant) are mixed and fusion; The oily solution that obtains is thus stirred also emulsification (as using homogenizer) with for example about 100 ℃ aqueous medium that is heated to that adds gradually; In addition, make potpourri carry out inversion of phases emulsification, can also optionally add surfactant if desired by adding aqueous medium.

In addition, but but its scope comprises the catalyzer of polycondensation catalyst/condensation catalyst is generally used for the polycondensation reaction/condensation reaction of the polycondensation monomer/condensation compound under the low temperature.The preference that has active catalyzer at low temperature comprises catalyzer and the hydrolytic enzyme that has surface-active acid, contains rare earth metal.By using these catalyzer, make polycondensation reaction/condensation reaction can be in aqueous medium under all 100 ℃ or lower conventional temperature according to appointment, carry out.For the process of accelerating polycondensation/condensation reaction or in order to use the more monomer of wide region, polycondensation/condensation can be carried out in the aqueous medium that is heated to about 100 ℃ or higher temperature.

Acid with surfactant character is the acid that has emulsification function and catalysis simultaneously, and described acid has by hydrophobic grouping and to small part and has the chemical constitution that hydrophilic radical constituted of Bronsted acid structure.Preference with acid of surfactant properties comprises such as alkyl benzene sulphonates such as dodecylbenzene sulfonic acid, cumene sulfonic acid, keryl benzene sulfonic acid or camphorsulfonic acids; Alkylsurfuric acid; The alkyl disulfonic acid; Alkylphenol sulfonic acid; Alkyl naphthalene sulfonic acid; Alkyl tetralin sulfonic acid; The alkyl allyl sulphonic acid; Mahogany acid; Alkyl benzimidazole sulfonic acid; The higher alcohol ether sulfonic acid; Alkyl diphenyl base sulfonic acid; Monobutyl phenylphenol sulfonic acid; Dibutyl phenylphenol sulfonic acid; Such as senior fatty acid sulfates such as laurilsulfates; Higher alcohol sulfate; Higher alcohol sulfate; High fatty acid amide alkyl sulfur acid esters; High fatty acid amide alkyl sulfur acid esters; Naphthenyl alcohol sulfuric acid; Sulphation fatty acid; Sulfosuccinate; Various fatty acid; The sulfonation higher fatty acid; The senior alkyl phosphate; Geocerellite; Resin acid alcohol sulfuric acid; Naphthenic acid; And salt etc.These acid with surfactant properties can be used in combination as required.

The example that contains the element that is comprised in the catalyzer of rare earth metal comprises lanthanide series such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu) etc.The particularly preferred example that contains the catalyzer of rare earth metal comprises alkyl benzene sulfonate, alkyl sulfate salt and the compound with fluoroform sulphonate structure.This metal trifluoroacetate mesylate is preferably the (OSO by structural formula X ₂CF ₃) ₃Represented compound, wherein X is scandium (Sc), yttrium (Y), ytterbium (Yb) or samarium (Sm) etc.

The group of the lanthanides fluoroform sulphonate is also advantageously as the catalyzer that contains rare earth metal.At J.Soc.Syn.Org.Chem. the 53rd volume (5), the group of the lanthanides fluoroform sulphonate is described in detail in the 44th～54 page.

As long as can the catalysis ester synthesis reaction, then hydrolytic enzyme be particularly limited.The example of hydrolytic enzyme comprises the esterase of classifying in 3.1 groups of EC (enzyme code), such as Carboxylesterase, lipase, phosphide enzyme, acetylesterase, pectinesterase, cholesterol esterase, tannase, monoacylglycerol lipase, lactonase or lipoprotein lipase (writing Asakura Publishing Company Ltd. (1982) or other documents referring to " Enzyme Handbook " Maruo and Tamiya); With the hydrolytic enzyme of classification in the EC3.2 group of glycosyl compound reaction, such as glucosidase, galactosidase, glucuronidase or xylosidase; Classify hydrolytic enzyme in EC3.3 group is such as epoxide hydratase; With the hydrolytic enzyme of classification in the EC3.4 group of peptide bond reaction, such as aminopeptidase, chymotrypsin, pancreatic enzyme, plasmin or optically-active subtilopeptidase A; Classify hydrolytic enzyme in EC3.7 group, such as the phloretin hydrase, or the like.

In these esterases, can hydrolysis glyceride and the enzyme spy that discharges fatty acid be called lipase.Lipase has the high stability that is included in the organic solvent, with the high activity of high yield catalysis ester synthesis reaction and many advantages such as availability cheaply.Thereby, consider from the angle of productive rate and cost, as the production of the polyester of following material according to condensation resin of the present invention/condensation compound particle, preferably use lipase for advantageously.

Can use the lipase in various sources.Its preference comprises the lipase that derives from such as microorganisms such as pseudomonad, Alcaligenes, achromobacter, Candida, Aspergillus, rhizopus or mucors; By the lipase that derives from various vegetable seedss; Derive from the lipase of animal tissue; Pancreatin, viokase etc.Wherein, the preferred lipase that derives from microorganisms such as pseudomonad, Candida or mould that uses.

These catalyzer can use separately also and can two or more be used in combination.

But the preference of employed condensation compound comprises carboxylic acid and alcohol in the dehydrating condensation process.But the exemplary of the condensation compound that obtains by the dehydrating condensation between carboxylic acid and alcohol is ester type waxes (ester compounds).

The preference of carboxylic acid comprises monocarboxylic acid and polybasic carboxylic acid.The example of monocarboxylic acid comprises myristic acid, palmitic acid, stearic acid, arachidic acid, mountain Yu acid, lignoceric acid, cerinic acid, montanic acid, melissic acid etc.

Polybasic carboxylic acid is the compound that contains two or more carboxyls in its molecule.Wherein, dicarboxylic acids is the compound that contains two carboxyls in its molecule, its example comprises oxalic acid, succinic acid, maleic acid, hexane diacid, the Beta-methyl hexane diacid, azelaic acid, decanedioic acid, the nonane dicarboxylic acid, decane dicarboxylic acid, heneicosane dicarboxylic acid, the dodecyl dicarboxylic acid, fumaric acid, citraconic acid, diglycolic acid, cyclohexane-3,5-diene-1, the 2-carboxylic acid, maleic acid, citric acid, hexahydroterephthalic acid, malonic acid, heptandioic acid, tartrate, galactosaccharic acid, phthalic acid, m-phthalic acid, terephthalic acid (TPA), tetrachlorophthalic acid, chlorophthalic acid, nitrophthalic acid, to carboxylphenylaceticacid acid, to phenylenediacetic Acid, between the benzene diglycolic acid, to the benzene diglycolic acid, adjacent benzene diglycolic acid, diphenyl acetic acid, diphenylene-right, to dicarboxylic acid, naphthalene-1, the 4-dicarboxylic acid, naphthalene-1, the 5-dicarboxylic acid, naphthalene 2, the 6-dicarboxylic acid, anthracene dicarboxylic acid etc.In addition, the example of the polybasic carboxylic acid except dibasic acid comprises trihemellitic acid, pyromellitic acid, naphthalene tricarboxylic acids, naphthalene tetracarboxylic acid, pyrene tricarboxylic acids, pyrene tetrabasic carboxylic acid etc.

On the other hand, alcohol comprises monohydroxy alcohol and dibasic alcohol or polyvalent alcohol.The example of monohydroxy alcohol comprises myristyl alcohol, cetanol, stearyl alcohol, arachidic alcohol, docosyl alcohol, tetracosanol, hexacosyl alcohol, octacosanol, melissyl alcohol etc.

In addition, the example of dibasic alcohol comprises ethylene glycol, propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexanediol, 1,10-decanediol, 1,12-dodecanediol, 1,14-tetradecane glycol, 1,16-hexadecane glycol, 1,18-octacosanol, 1,20-eicosane glycol, 1,30-triacontane glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, spiral shell glycol (spiroglycol), 1,4-Benzenediol, bisphenol-A, hydrogenated bisphenol A etc.The example of trihydroxy alcohol comprises 1,2,4-butantriol, 1,2,5-penta triol, 2-methyl isophthalic acid, 2,4-butantriol, glycerine, 2-methyl-prop triol, trimethylolethane, trihydroxyethyl ethane, trimethylolpropane, 1,3,5-trihydroxy methyl benzene etc.The example of tetra-atomic alcohol comprises 1,2,3, the own tetrol of 6-, pentaerythrite etc.The example of pentabasis alcohol comprises glucose etc., and the example of hexahydroxylic alcohols comprises dipentaerythritol etc.

In addition, the example of the polyvalent alcohol except above-mentioned dibasic alcohol (polyvalent alcohol) comprises hexamethylolmelamine, six hydroxyethyl melamines, tetra methylol benzoguanamine and four hydroxyethylbenzene substituted melamines etc.

But the preference of employed condensation compound comprises amine in the dehydration condensation.Speciogenesis dehydration in amine and the above-mentioned monocarboxylic acid can generate the crystal type acid amides as condensation compound.

The example of amine comprises following various monoamines and diamine.The example of diamine comprises ethylenediamine, two ethylenediamines, triethylenediamine, 1,2-propane diamine, 1,3-propane diamine, 1,4-butanediamine, 1,4-butylene diamines, 2,2-dimethyl-1,3-butanediamine, 1,5-pentanediamine, 1,6-hexane diamine, 1,4-cyclohexanediamine and 1,4-hexamethylene dimethylamine etc.

Resulting condensation compound is preferably crystal; Its fusing point preferably is about 50 ℃～120 ℃, is more preferably 50 ℃～100 ℃, further preferably is about 60 ℃～90 ℃.If condensation compound has too high fusing point, then will deterioration for aspects such as at low temperatures fixing performance of toner, the separation efficiency from the fixing roller, heat-resisting stained property.In addition,, then can make the plasticizing of the adhesive resin of sticking connection efficiency degradation, and make separation efficiency and the further deterioration of heat-resisting stained property from the fixing roller if condensation compound had low fusing point.

But the example of employed polycondensation monomer comprises polybasic carboxylic acid, polyvalent alcohol and polyamine in the polycondensation.But the particularly preferred example of polycondensation monomer comprises that those contain polybasic carboxylic acid and polyvalent alcohol so that the material of polyester to be provided.

But the example as the polybasic carboxylic acid of polycondensation monomer comprises the employed polybasic carboxylic acid in dehydrating condensation that those have exemplified.

But the preference that is used as the polybasic carboxylic acid of polycondensation monomer comprises azelaic acid, decanedioic acid, 1,9-nonane dicarboxylic acid, 1,10-decamethylene dicarboxylic acid, 1,11-heneicosane dicarboxylic acid, 1,12-dodecanedicarboxylic acid, terephthalic acid (TPA), trihemellitic acid and pyromellitic acid etc.These polybasic carboxylic acids are insoluble in water or water insoluble, so ester synthesis reaction is to carry out in the formed suspending liquid being dispersed in the water by polybasic carboxylic acid.

But in being used as the polyvalent alcohol of polycondensation monomer, the preference of dibasic alcohol comprises ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, hexanediol, cyclohexanediol, ethohexadiol, decanediol and dodecane alkane glycol etc.But the preference that is used as the polyvalent alcohol of polycondensation monomer except dibasic alcohol comprises glycerine, pentaerythrite, hexamethylolmelamine, six hydroxyethyl melamines, tetra methylol benzoguanamine and four hydroxyethylbenzene substituted melamines etc.

But the particularly preferred example that is used as the polyvalent alcohol of polycondensation monomer comprises such as 1 8-ethohexadiol, 1,10-decanediol and 1, dibasic alcohol such as 12-dodecanediol.These polyvalent alcohols are insoluble in water or water insoluble, thereby ester synthesis reaction is to carry out in the formed suspending liquid being dispersed in the water by polyvalent alcohol.

But can be easy to make amorphous resin and crystal type resin by making up these polycondensation monomers.

The example of employed polybasic carboxylic acid comprises oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, dodecyl succinic acid, Permethyl 99A base succinic acid, different dodecene base succinic acid, n-octyl succinic acid, positive ocentyl succinic and acid anhydrides or acid chloride when preparation crystal type polyester or polyamide.

The example of employed polyvalent alcohol comprises ethylene glycol, diethylene glycol, triethylene glycol, 1 when preparation crystal type vibrin, 2-propylene glycol, 1, ammediol, 1,4-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1, the bisphenol-A of 4-cyclohexanedimethanol, dipropylene glycol, polyglycol, polypropylene glycol, polytetramethylene glycol, bisphenol-A, bisphenol Z and hydrogenation etc.

The example of employed polyamines comprises ethylenediamine, two ethylenediamines, triethylenediamine, 1 when the preparation polyamide, 2-propane diamine, 1,3-propane diamine, 1,4-butanediamine, 1,4-butylene diamines, 2,2-dimethyl-1,3-butanediamine, 1,5-pentanediamine, 1,6-hexane diamine, 1,4-cyclohexanediamine and 1,4-hexamethylene dimethylamine etc.

But the condensation resin that is obtained by the polycondensation monomer polycondensation is preferably crystal.The use of crystal type condensation resin can make the low-temperature fixing of toner be more prone to.

The example of this crystal type vibrin comprises by 1, and 9-nonanediol and 1,10-decamethylene dicarboxylic acid react or react resulting polyester by cyclohexanediol and hexane diacid; By 1,6-hexanediol and decanedioic acid reaction resulting polyester; By ethylene glycol and succinic acid reaction resulting polyester; By ethylene glycol and decanedioic acid reaction resulting polyester; And by 1,4-butylene glycol and succinate reaction resulting polyester.Wherein, more preferably by 1,9-nonanediol and 1,10-decamethylene dicarboxylic acid react resulting polyester and by 1,6-hexanediol and decanedioic acid react resulting polyester.

The fusing point T of crystal type condensation resin _mScope be about 50 ℃～120 ℃, preferably be about 55 ℃～90 ℃.Because this bounding force in high temperature range of adhesive resin descends, so T _mBe lower than the deterioration that 50 ℃ resin can cause release efficiency in the fixing.T _mThe resin that is higher than 120 ℃ can cause fusion insufficient, and this can cause the rising of minimum fixing temperature.

In the present invention, can determine the fusing point of crystal type resin by the peak value melt temperature that input-compensation differential scanning calorimetry (DSC) is measured the temperature programme speed with 10 ℃ of per minutes rises to 150 ℃ process from room temperature according to known method.The crystal type resin has a plurality of melting peaks usually, yet, in the present invention, the maximum peak in the DCS measurement is considered as fusing point.In addition, the glass transition temperature of amorphous resin is the value of being measured by as the differential scanning calorimetry of being explained in detail among the ASTM D3418-82 (DSC).

On the other hand, the glass transition temperature T of amorphous condensation resin particle _gPreferably be about 50 ℃～80 ℃, be more preferably 50 ℃～65 ℃.Because the deterioration of this bounding force in high temperature range of adhesive resin, so T _gBeing lower than about 50 ℃ resin can cause frequent hot stained in fixing.T _gBe higher than the rising that about 80 ℃ resin can cause minimum fixing temperature because of fusion is insufficient.

But the scope of the weight-average molecular weight of the condensation resin that the polycondensation by polycondensation monomer makes is about 1500～60000, preferably is about 3000～40000.Because the decline of the bounding force of bonding agent and interlaminar resin, weight-average molecular weight are lower than the deterioration that 1500 resin can cause hot stained character.Weight-average molecular weight is higher than that 60000 resin has good hot stained character but the rising that can cause minimum fixing temperature.Condensation resin can comprise part branched structure and cross-linked structure etc., and this depends on the carboxylic acid of used monomer and first number of alcohol.

But the median particle diameter of the condensation resin that the polycondensation reaction by polycondensation monomer makes preferably is about 10 microns or littler, is more preferably 7 microns or littler; Be most preferably 1 micron or littler.When as toner, owing to comprise the deterioration of the picture quality character of resolution, so particle diameter is disadvantageous greater than about 10 microns resin.In addition, because the increase deficiency of molecular weight and speed during the preparation, and consider the quality and the intensity of image after the photographic fixing, particle diameter is disadvantageous greater than about 10 microns resin.

For in aqueous medium, make have decide the condensation resin particle of particle diameter, heterophase polymerization system in the aqueous medium commonly used is such as suspension polymerization, solubilising dispersion method, microemulsion method, micro emulsion method, huge newborn method (macroemusion method), multistage expansion method or comprise that the emulsion polymerization of seeding polymerization can be used as polymerization.In addition, in the case, because it is 1 micron or littler particle that its manufacture can obtain diameter, therefore can provide diameter be 1 micron or littler nanometer size particles be preferred such as polymerizations such as microemulsion method or micro emulsion methods, described particle diameter is most preferred, this is the result because of polycondensation reaction, and particularly final molecular weight and polymerization rate depend on the ultimate size of aforesaid particle and the efficient in the production run.

But when but the polycondensation reaction/dehydration condensation of polycondensation monomer/condensation compound carries out in aqueous medium, by for example using mechanical shear stress or ultrasound wave can make above-mentioned each material emulsification and being dispersed in the aqueous medium.In emulsification and dispersion process, surfactant, polymeric dispersant or inorganic dispersant etc. can be added in the aqueous medium as required.

The example of employed surfactant comprises such as anionic surfactants such as sulfuric acid, sulfonate or phosphates among the present invention; Such as cationic surfactants such as amine salt or quaternary amines; Such as non-ionic surfactants such as polyglycol, alkylphenol ethylene oxide adduct or polyvalent alcohols.Wherein, preferred anionic and cationic surfactant.Non-ionic surfactant preferably is used in combination with anionic and cationic surfactant.Surfactant can use separately or two or more is used in combination.Examples of anionic surfactants comprises neopelex, sodium alkyl naphthalene sulfonate, aryl alkyl polyethers sodium sulfonate, 3,3-disulfo-acardite-4,4-diazo-two-amido-8-naphthol-6-sulfonic acid sodium, adjacent carboxyl benzene-azo-xylidin, 2,2,5,5-tetramethyl-triphenyl methane-4,4-diazo-two-betanaphthol-6-sodium sulfonate, dialkyl sodium sulfosuccinate, lauryl sodium sulfate, sodium tetradecyl sulfate, pentadecyl sodium sulphate, sodium octyl sulfate, sodium oleate, sodium laurate, sodium caprate, Sodium Caprylate, sodium n-caproate, potassium stearate and calcium oleate etc.The example of cationic surfactant comprises chlorination alkyl phenyl Dimethyl Ammonium, chlorination alkyltrimethylammonium and chlorination two (octadecyl) ammonium etc.The example of non-ionic surfactant comprises the combination of polyethylene oxide, polypropyleneoxide, polypropyleneoxide and polyethylene oxide, the ester that derives from polyglycol and higher fatty acid, alkylphenol polyethylene oxide, the ester that derives from higher fatty acid and polyglycol, the ester that derives from higher fatty acid and polypropyleneoxide and sorbitan ester etc.In addition, the example of polymeric dispersant comprises poly carboxylic acid sodium and polyvinyl alcohol (PVA) etc.; The example of inorganic dispersant comprises lime carbonate etc., but the present invention is not limited thereto.For preventing the Ostwald ripening phenomenon of monomer emulsion particle in the aqueous medium, can add by the higher alcohol of enanthol and octanol representative, by senior aliphatic hydrocarbon of hexadecane representative etc. as stabilization additives.

But when in aqueous medium, carrying out the polycondensation reaction of polycondensation monomer, can be with such as colorant, be added in the aqueous medium in advance and along with polycondensation process is incorporated in the condensation resin particle such as common employed composition in the toners such as fixing aids such as wax, charged adjuvant.

The production method of electrostatic image-developing toner

The production method of electrostatic image-developing toner of the present invention comprises: the particle in the dispersion liquid of the particulate resin dispersion that wherein contains condensation resin particle of the present invention at least by condensing or condensation compound particle of the present invention and resin particle comes aggregated particle (accumulation process); By heating the particle (condensation process) that condenses and assembled.Described autofrettage is included into the method that emulsion polymerization is assembled that is commonly referred to.

In accumulation process, will in aqueous medium, produce according to condensation resin particle of the present invention or condensation compound particle according to the present invention, thereby products obtained therefrom can directly be used as dispersion liquid.In the case of necessary,, condense, can make aggregated particle with the diameter that is applicable to toner to wherein adding coagulator and these particles being mixed by described particle dispersion is mixed with coloring agent particle dispersion liquid or releasing agent particle dispersion.In addition, by in aforesaid way, forming first aggregated particle, to wherein adding, can cover described particle then with shell according to particulate resin dispersion of the present invention or other particulate resin dispersion.Though the coloring agent particle dispersion liquid is preparation separately in this example, if colorant is added in the condensation resin particle in advance, then this colorant dispersion is optional.

After finishing gathering, the particle that condenses and assembled by heating under the temperature of the glass transition temperature that is higher than resin particle cleans on demand, and carry out drying (fusion/condensation process) in condensing, to produce toner.

Finish condense after, the required toner-particle of processing in cleaning process, solid-liquid detachment process and dry run arbitrarily; Consider the charged character of gained toner, preferably thoroughly wash this particle with ion exchange water.Detachment process is not particularly limited to solid-liquid, but from the viewpoint of throughput rate, preferably attract or add depress overanxious.In addition, dry run is not particularly limited, but from the viewpoint of throughput rate, preferably freeze drying, dodge that spray is dry, fluidized bed drying and vibra fluidized bed drying etc.

Below, will each composition (producing employed material) of toner be described.

Except surfactant, preferably with inorganic salts or divalence or the slaine more than the divalence as coagulator.Particularly, consider and assemble control and the charged efficient of toner, preferably use slaine.Dispersion, gathering and own aggregated particle stable etc. that surfactant can be used in addition, dispersion, the releasing agent of emulsion polymerization, dispersing of pigments, resin particle such as resin.Particularly, to be effectively with using such as anionic surfactant such as sulfuric acid, sulfonate, phosphate or soap or such as cationic surfactants such as amine salt or quaternary ammonium salts, such as the rotational shear homogenizer, adopt bowl mill, the sand mill of medium or wear promise mill any dispersion means commonly used such as (Dynomill dynomill) and all can be used as the dispersion means such as nonionic surfactant combinations such as polyglycol, alkylphenol ethylene oxide adduct or polyvalent alcohols.

Particularly, when using according to condensation resin particle dispersion of the present invention, for example the additional polymerized resin particle dispersion liquid by known emulsion polymerization preparation can be used in combination with the condensation resin particle dispersion.

The example that is used to produce the additional polymerisable monomer of these particulate resin dispersions comprises the homopolymer and the multipolymer of vinyl monomer, and its example comprises such as styrene or to phenylethylene materials such as chlorostyrenes; Such as vinyl acetate such as vinylnaphthalene, vinyl chloride, bromine ethene, fluorothene, vinyl acetate, propionate, vinyl benzoate or vinyl butyrates; Such as methylene aliphatic carboxylic acid esters,s such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid dodecane ester, acrylic acid n-octyl, acrylic acid-2-chloro ethyl ester, phenyl acrylate, acrylic acid-alpha-chloro ethyl ester, methyl methacrylate, Jia Jibingxisuanyizhi or butyl methacrylates; Vinyl cyanide; Methacrylonitrile; Acrylamide; Such as vinyl ether such as vinyl methyl ether, EVE or vinyl isobutyl ethers; Has the monomer that contains the N polar group such as N-vinyl compound that comprises N-ethene pyrroles, N-vinyl carbazole, N-ethene indoles and N-ethene pyrrolin etc.; Such as vinyl carboxylic acids such as methacrylic acid, acrylic acid, cinnamic acid or acrylic acid carboxyl ethyl esters, or the like.In addition, various waxes can also be used in combination with it.

When using additional polymerization single polymerization monomer, particulate resin dispersion can prepare by emulsion polymerization in the presence of ionic surfactant; Or alternatively, when using another kind of resin, by resin being dissolved in oil-based solvent (when resin is water insoluble relatively when being dissolved in oil-based solvent), and by using such as decollators such as homogenizers resin and ionic surfactant or the polymer dielectric form with particle is dispersed in the aqueous medium, then by heating or removal of solvent under reduced pressure is produced particulate resin dispersion.

Particularly, in order to reach the purpose of low-temperature fixing, preferably use the crystal type resin as the employed resin of resin particle (adhesive resin) in the particle dispersion that contains with good grounds condensation compound particle of the present invention and resin particle.

The crystal type resin is preferably the crystal type vibrin, more preferably has the aliphatics crystal type vibrin of suitable fusing point.Hereinafter will be described as an example with the crystal type vibrin.

The crystal type aliphatic polyester comprises the polyester of making such as by ring-opening polymerization such as polycaprolactone; Yet many polyester are by acid (dicarboxylic acid) composition and the preparation of alcohol (glycol) composition.In the present invention, term " acid derive composition " is to be the composition of acid before prepared vibrin by it in preparation, and term " alcohol derive composition " is to be the composition of alcohol before prepared vibrin by it in preparation.

If vibrin is a non-crystalline type, promptly amorphous, then when keeping suitable low-temperature fixing character, can't by toner provide the suitable anti-adhesive of toner and the stability of storage image.Therefore, in the present invention, " crystal type vibrin " is in the thermal absorption in differential scanning calorimetry (DSC), has significant endothermic peak, rather than the resin of stepped, if supplementary element is copolymerized in the main chain of crystal type polyester, then supplementary element content is that the multipolymer that is less than or equal to about 50 weight % is also referred to as the crystal type polyester.

The acid composition of deriving is preferably aliphatic dicarboxylic acid, particularly the straight-chain carboxylic acid.Its preference includes but not limited to oxalic acid, malonic acid, succinic acid, glutaric acid, hexane diacid, heptandioic acid, suberic acid, azelaic acid, decanedioic acid, 1,9-nonane dicarboxylic acid, 1,10-decane dicarboxylic acid, 1,11-heneicosane dicarboxylic acid, 1,12-dodecanedicarboxylic acid, 1,13-astrotone, 1,14-tetradecane dicarboxylic acid, 1,16-hexadecane dicarboxylic acid, 1,18-octadecane dicarboxylic acid and lower alkyl esters thereof or acid anhydrides.

Derive dicarboxylic acid that the preference of composition comprises that the dicarboxylic acid with two keys is derived composition and had one or more sulfonic acid groups of acid except aliphatic dicarboxylic acid is derivatized to branch is derivatized to and grades.

Dicarboxylic acid with two keys derive the example of composition comprise derived from the composition of dicarboxylic acid with two keys with become to grade derived from the lower alkyl esters of dicarboxylic acid or acid anhydrides with two keys.In addition, the dicarboxylic acid with sulfonic acid group derive the example of composition comprise derived from the composition of dicarboxylic acid with sulfonic acid group with become to grade derived from the lower member ester of dicarboxylic acid or acid anhydrides with sulfonic acid group.

Owing to utilize two bond energys enough to make all resin crosslinks, the therefore preferred dicarboxylic acid with two keys that uses prevents hot stained in the photographic fixing.The example of this dicarboxylic acid includes but not limited to fumaric acid, maleic acid, 3-hexene diacid, 3-octendioic acid, its lower alkyl esters and its acid anhydrides etc.Wherein, consider preferred fumaric acid and maleic acid etc. from the angle of cost.

Dicarboxylic acid with sulfonic acid group can effectively disperse such as colorants such as pigment.As described below, when by with particle emulsification or when disperseing to prepare toner-particle in water, the existence of sulfonic acid group can impel emulsification or dispersion and need not to use surfactant.Example with dicarboxylic acid of sulfonic acid group includes but not limited to that the 2-sulfo group is to Sodium Benzoate, 5-sulfosalicylic phthalate sodium, sodium sulfosuccinate, its lower alkyl esters and its acid anhydrides etc.Wherein, consider cost, preferably use 5-sulfosalicylic phthalate sodium etc.

Except the acid that aliphatic dicarboxylic acid is derivatized to is exceptionally derived composition (promptly, the dicarboxylic acid that dicarboxylic acid with two keys is derived composition and/or had the sulfonic acid group composition of deriving) constitutes a mole %～20 and constitute mole % than preferably being about 1 with respect to the derive content of composition of acid, be more preferably 2 and constitute mole %～10 and constitute mole %.

When content constitutes mole % less than about 1, then owing to, can make the diameter of controlling toner by condensing become difficult such as the insufficient dispersion of pigment and the problems such as diameter increase of emulsified particles.On the other hand, when content surpasses 20 formation mole %, the deterioration that the image fastness then occurs, and because the emulsified particles that its too small diameter caused solubilising and can't make latex in water owing to problems such as the decline of vibrin crystallinity and fusing point reductions.

In the present invention, when the content of each composition (acid derive composition or alcohol derive composition) was expressed by unit (mole), term " constituted a mole % " and is meant the number percent of each composition in the vibrin.

The alcohol composition is preferably aliphatic diol, and its preference includes but not limited to ethylene glycol, 1, ammediol, 1,4-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptandiol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane glycol, 1,12-dodecanediol, 1,13-tridecane glycol, 1,14-tetradecane glycol, 1,18-octacosanol and 1,20-eicosane glycol etc.

When the alcohol composition of deriving is that aliphatic diol is derivatized to timesharing, with respect to whole alcohol composition of deriving, aliphatic diol is derived the content of composition than for constituting mole % more than or equal to about 80, and can also contain other additional compositions if desired.When the alcohol composition of deriving is that aliphatic diol is derivatized to timesharing, with respect to whole alcohol composition of deriving, the derive content ratio of composition of aliphatic diol is preferably more than or equals about 90 and constitutes mole %.

Be lower than about 80 and constitute in the situation of mole % at the derive content of composition of aliphatic diol, because the decline of vibrin crystallinity and the reduction of fusing point, then deterioration all can take place in the stability and the low-temperature fixing character of the anti-adhesive of toner, institute's memory image.

The example of other compositions that contain comprises that the glycol with one or more pairs of keys is derived composition, glycol with one or more sulfonic acid groups is derived composition as required.

Example with glycol of one or more pairs of keys comprises the 2-butene-1,4-glycol, 3-butene-1,6-two pure and mild 4-butene-1s, 8-glycol etc.Example with glycol of one or more sulfonic acid groups comprises 1,4-dihydroxy-2-benzene sulfonic acid sodium salt, 1,3-dihydroxymethyl-5-benzene sulfonic acid sodium salt and 2-sulfo group-1,4-butylene glycol sodium etc.

Be derivatized to timesharing when adding the derive alcohol of composition of non-straight chain aliphatic diols, promptly, the glycol that the glycol that has two keys when adding is derived composition and/or had a sulfonic acid group is derivatized to timesharing, with respect to whole alcohol composition of deriving, the derive content of composition of the glycol that glycol with two keys is derived composition and/or had a sulfonic acid group constitutes a mole %～20 and constitutes mole % than preferably being about 1, is more preferably 2 and constitutes mole %～10 and constitute mole %.

Be lower than 1 when constituting mole % when the alcohol except that straight chain aliphatic diols is derivatized to branch is derivatized to branch with respect to the derive content ratio of composition of whole alcohol, then since the problems such as increase of insufficient dispersion of pigment or emulsified particles diameter can cause by assembling the diameter of the controlling toner difficulty that becomes.On the other hand, when this content ratio constitutes mole % greater than 20, the deterioration that the image fastness then occurs, and because the emulsified particles that its too small diameter caused solubilising and can't make latex in water owing to problems such as the decline of vibrin crystallinity and fusing point reductions.

Production method to vibrin is not particularly limited, and can adopt the polyester method of the reaction of sour composition of known utilization and pure composition.Its example comprises direct polycondensation and transesterification etc., or also can select according to the kind of used monomer.Because sour composition changes with the reaction conditions that is adopted etc. with respect to the mol ratio (sour composition/pure composition) of pure composition, thereby can not determine its mol ratio usually, yet mol ratio is about 1/1 usually.

Vibrin can be produced in 180 ℃～230 ℃ polymerization temperature.In the polyester resin production process, water and the alcohol under reduced pressure removing condensation reaction as required and generated carry out condensation reaction simultaneously.

If monomer is insoluble each other or incompatible under temperature of reaction, then carry out the monomer solubilising by the high boiling solvent that adds as solubilizer.When solubilizer is steamed, carry out polycondensation reaction.If in copolyreaction, there is the relatively poor monomer of compatibility, then with principal ingredient generation polycondensation before, the monomer that this intermiscibility is relatively poor in advance with will carry out condensation with the acid or the alcohol of monomer polycondensation.

The example of employed catalyzer comprises such as alkali metal compounds such as sodium compound or lithium compounds when producing vibrin; Such as alkaline earth metal compounds such as magnesium compound or calcium compounds; Metallic compounds such as compound such as zinc, magnesium, antimony, titanium, tin, zirconium or germanium; Phosphorons acid compound; Phosphate cpd and amines etc.Its exemplary comprises sodium acetate, sodium carbonate, lithium acetate, lithium carbonate, calcium acetate, calcium stearate, magnesium acetate, zinc acetate, zinc stearate, zinc naphthenate, zinc chloride, magnesium acetate, magnesium naphthenate, purity titanium tetraethoxide, four titanium propanolates, tetraisopropoxy titanium, four titanium butoxide, antimony trioxide, antimony triphenyl, tributyl antimony, formic acid tin, tin oxalate, tetraphenyltin, the dichloride dibutyl tin, dibutyltin oxide, diphenyl tin oxide, tetrabutyl zirconate, zirconium naphthenate, zirconyl carbonate, zirconyl acetate, zirconyl stearate, zirconyl octoate, germanium oxide, triphenyl phosphite, three (2,4-two-tert-butyl-phenyl) phosphite ester, bromination ethyl triphenyl phosphine, triethylamine and triphenylamine etc.

For further with its modification, other extra resins and above-mentioned resin combination can be used, its example as adhesive resin comprises the homopolymer and the multipolymer of vinyl monomer, and its example comprises such as vinyl acetate such as vinylnaphthalene, vinyl chloride, bromine ethene, fluorothene, vinyl acetate, propionate, vinyl benzoate or vinyl butyrates; Such as methylene aliphatic carboxylic acid esters,s such as methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, acrylic acid dodecane ester, acrylic acid n-octyl, acrylic acid-2-chloro ethyl ester, phenyl acrylate, acrylic acid-alpha-chloro ethyl ester, methyl methacrylate, Jia Jibingxisuanyizhi or butyl methacrylates; Vinyl cyanide; Methacrylonitrile; Acrylamide; Such as vinyl ether such as vinyl methyl ether, EVE or vinyl isobutyl ethers; Has the monomer that contains the N polar group such as N-vinyl compound that comprises N-ethene pyrroles, N-vinyl carbazole, N-ethene indoles or N-ethene pyrrolin etc.; Such as vinyl carboxylic acids such as methacrylic acid, acrylic acid, cinnamic acid or acrylic acid carboxyl ethyl esters, or the like.In addition, various waxes can also be used in combination with it.

If form other resins by vinyl monomer, then its particulate resin dispersion can be produced by emulsion polymerization in the presence of ionic surfactant etc.If form other resins by the monomer except vinyl monomer, then when resin can be dissolved in relative water-immiscible solvent, its particulate resin dispersion can be by being dissolved in resin in the oil-based solvent, in aqueous medium, utilize and solution is disperseed to become graininess with ionic surfactant or polyeletrolyte, produce by heating or removal of solvent under reduced pressure then such as decollators such as homogenizers.

When the formation resin of resin particle when being amorphous, its glass transition temperature T _gScope be about 50 ℃～80 ℃, preferably be about 50 ℃～65 ℃.Because the deterioration of this bounding force in high temperature range of adhesive resin, so T _gBeing lower than about 50 ℃ resin can cause frequent hot stained in fixing.T _gBe higher than the rising that about 80 ℃ resin can cause minimum fixing temperature because of fusion is insufficient.

Alternatively, if the formation resin of resin particle is a crystal type, the crystalline melting point T of resin then _mScope be about 50 ℃～120 ℃, preferably be about 55 ℃～90 ℃.T when resin _mWhen being lower than 50 ℃, can cause this bounding force in high temperature range of adhesive resin to descend, thereby cause the deterioration of release efficiency in the fixing and more frequent hot stained; T when resin _mWhen being higher than 120 ℃, can cause inadequate fusion, thereby cause the rising of the minimum fixing temperature of toner.

The mean diameter of resin particle is about 1 micron or littler usually, preferably is about 0.01 micron～1 micron.When the mean diameter of particle during, because therefore gained electrostatic image-developing toner particle grain size distribution expansion and generated free particles is easy to cause the deterioration of toner performance and reliability greater than about 1 micron.On the other hand, during mean diameter in particle has above-mentioned scope, because particle is without any the problems referred to above, the quantity variance of the resin particle that each toner-particle contained reduces, resin particle more is evenly distributed in each toner-particle, thereby the fluctuation of the performance of toner and reliability is littler, is favourable therefore.Mean diameter can be used such as coulter counter and measure.

The mean diameter of resin particle (median particle diameter) is about 1 micron or littler, preferably is about 50 nanometers～400 nanometers, is more preferably 70 nanometers～350 nanometers.The mean diameter of resin particle (median particle diameter) can be by such as laser diffraction granularity analyzer (trade name: above-mentioned LA-920) measure.

The example of the dispersion solvent of resin particle comprises aqueous medium and organic solvent.The example of aqueous medium comprises such as water and alcohols such as distilled water, ion exchange waters.These dispersion solvents can use separately or two or more is used in combination.Aqueous medium preferably contains surfactant.Surfactant is not particularly limited, and its example comprises such as anionic surfactants such as sulfuric acid, sulfonate, phosphate or soap; Such as cationic surfactants such as amine salt or quaternary ammonium salts; Such as non-ionic surfactants such as polyglycol, alkylphenol ethylene oxide adduct or polyvalent alcohols, or the like.Wherein, preferred anionic surfactant and cationic surfactant.Non-ionic surfactant preferably is used in combination with anionic surfactant or cationic surfactant.Described surfactant can use separately, also can two or more be used in combination.

The object lesson of anionic surfactant comprises lauryl sodium sulfate, lauryl sodium sulfate, sodium alkyl naphthalene sulfonate and dialkyl sodium sulfosuccinate etc.The object lesson of cationic surfactant comprises chlorination alkyl phenyl dimethylammonium, chlorination alkyltrimethylammonium and chlorination two (octadecyl ammonium etc.。

Representative examples of organic comprises ethyl acetate and toluene.Organic solvent is suitably selected according to employed adhesive resin.

When resin particle is vinylite, this vinylite is homopolymer or the multipolymer such as the ester monomers such as ester with vinyl, ethene nitrile, vinethene or ketenes etc., and emulsion polymerization by for example vinyl monomer in containing the solvent of ionic surfactant or seeding polymerization can be manufactured on the homopolymer that contains vinyl monomer (vinylite) in the solvent that comprises ionic surfactant or the dispersion liquid of multipolymer.

If resin particle is the homopolymer of non-vinyl monomer or the resin of multipolymer, if resin can be dissolved in relative water-immiscible solvent, by resin particle is dissolved in the oil-based solvent, in aqueous medium, utilize decollator such as homogenizer that this solution and ionic surfactant or polyeletrolyte are together disperseed forming particulate form, and by heating or under reduced pressure boil off the dispersion liquid that oil-based solvent prepares the resin particle of the resin that contains non-vinylite in comprising the solvent of ionic surfactant.

Alternatively, if resin particle is crystal type polyester or amorphous polyester resin, then can produce aqueous liquid dispersion by the effect stabilization of aqueous medium, wherein resin particle has the functional group that can become cationic form by neutralization, in water, have from dispersed, and its part or all of hydrophilic functional groups can neutralize with alkali.In crystal type polyester and amorphous polyester resin, the functional group that can become hydrophilic by neutralization is such as carboxylic acid or sulfonic acidic-group.Therefore, the example of operable neutralizing agent comprises such as inorganic bases such as NaOH, potassium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate or ammoniacal liquor; Such as organic bases such as diethylamine, triethylamine or isopropylamines.

If the vibrin that will in water, can not disperse, promptly, non-from water-dispersed resin, during as resin particle, by with resin solution and/or aqueous medium and easily mixed with it together disperseing such as the acid of ionic surfactant, polymerization or the polyeletrolytes such as alkali of polymerization, in the temperature that is equal to or higher than melting point resin potpourri is heated, and extrude dispersion machine with homogenizer or high pressure and under high shear process this potpourri, can be easy to make about 1 micron or littler particle.When using ionic surface active agent or polymer dielectric, be that the amount of 0.5 weight %～5 weight % adds described ionic surface active agent or polyeletrolyte preferably with the concentration in aqueous medium.

Following colorant can be used as colorant.The example of black pigment comprises carbon black, cupric oxide, manganese dioxide, nigrosine, acticarbon, non magnetic limonite and magnetic iron ore etc.The example of yellow uitramarine comprises chrome yellow, zinc yellow, iron oxide yellow, cadmium yellow, chrome yellow, Hansa yellow, Hansa yellow-10G, benzidine yellow G, benzidine yellow G R, threne Huang, quinoline yellow and permanent yellow NCG etc.The example of orange pigment comprises red chrome yellow, molybdate orange, permanent orange GTR, pyrazolone orange, Fu Erken orange, Benzidine orange G, indanthrene brilliant orange RK and indanthrene brilliant orange GK etc.The example of red pigment comprise colcother, cadmium red, red lead, mercuric sulphide, C lake red CAN'T, permanent red 4R, lithol red, bright fuchsin 3B, bright fuchsin 6B, Du Pont's oil red, pyrazolone red, rhodamine B lake, lake red C, rose-red, eoxine is red and alizarine lake etc.The example of blue pigment comprises barba hispanica, cobalt blue, alkali blue lake, Victoria blue color lake, sun-proof peacock blue (Fast Sky blue), indanthrene blue BC, aniline blue, ultramarine blue, Calco oil blue, methylene chloride indigo plant, phthalocyanine blue, the phthalein mountain valley with clumps of trees and bamboo is green and peacock green oxalates etc.The example of violet pigment comprises manganese violet, the purple B of sun-proof and methyl violet color lake etc.The example of viridine green comprises that chromium oxide, chrome green, pigment are green, peacock green color lake and yellowish green G (Final yellow greenG) etc. eventually.The example of Chinese white comprises zinc white, titanium dioxide, stibium trioxide and zinc sulphide etc.The example of extender pigment comprises ground barium sulfate, barium carbonate, clay, silica, hard charcoal, mica and alumina white etc.In addition, the example of dyestuff comprises such as various dyestuffs such as basic-dyeable fibre, acid dyes, dispersion liquid dyestuff and direct dyess, and its object lesson comprises nigrosine, methylenum careuleum, rose-red, quinoline yellow and ultramarine blue etc.

These colorants can be used singly or in combination.The dispersion liquid of coloring agent particle can prepare by following equipment: the dispersion machine that contains dispersion medium such as rotational shear homogenizer, bowl mill, sand mill or masher etc.; High pressure subtend conflict formula dispersion machine etc.Alternatively, these colorants can be dispersed in the water in the presence of the surfactant with polarity with homogenizer.

Consider suitably to select colorant from hue angle, color saturation, brightness, weatherability, overhead projector's (OHP) transparency and dispersed angle.

With respect to the general assembly (TW) of solid content in the toner, the addition of colorant is 4 weight %～15 weight %.What make an exception is that when using magnetic-particle as black colorant, with respect to the general assembly (TW) of solid content in the toner, the addition of magnetic-particle is 12 weight %～50 weight %.

When with toner fixing, the use level of this colorant must be able to be guaranteed the color density of this moment.In addition, be adjusted into 100 nanometers～330 nanometers, can guarantee the OHP transparency and the color density of the image that forms by mean diameter (median particle diameter) with the coloring agent particle in the toner.

Can use such as laser diffraction granularity analyzer (trade name: above-mentioned LA-920) measure the mean diameter (median particle diameter) of coloring agent particle.

When using toner according to the present invention as magnetic color tuner, can be to wherein adding Magnaglo.Particularly, use magnetized material in magnetic field, its example comprises the ferromagnetic powder such as iron, cobalt and nickel etc.; Such as compounds such as limonite and magnetic iron ore.When aqueous phase prepares toner, note the migration of magnetic material to water.Preferably by such as the hydrophilic treatment surface of modified magnetic material in advance.

In addition, internal additive, for example magnetic material can be selected from such as ferrite, magnetic iron ore, reduced iron, cobalt, nickel or metals such as magnesium and alloy thereof, or contains the compound of these metals.Antistatic agent, the nigrosine compound also can be used as internal additive by the dyestuff or the triphenyl methane pigment of the complex compound of aluminium, iron or chromium preparation, and wherein said antistatic agent is selected from such as various antistatic agent commonly used such as quaternary ammonium salts.Consider influence in condensation process is condensed and the ionic strength of melting efficiency is controlled, and reduce contaminated wastewater, internal additive is preferably almost water-fast material.

The object lesson of releasing agent comprises various ester type waxes: such as low-molecular-weight polyolefins such as tygon, polypropylene or polybutylene; The silicone that occurs softening point by heating; Such as fatty acid amides such as oleamide, sinapic acid acid amides, ricinoleic acid acid amides or stearic amides; Such as Brazil wax, rice wax, candelila wax, Japan wax, and jojoba wet goods vegetable wax; Such as animal waxs such as beeswaxs; Such as mineral-pertroleum waxes such as montan wax, ceresine, ceresin, paraffin, microcrystalline wax or Fischer-Tropsch waxes; And material modified etc.

These waxes are difficult near room temperature or are dissolved in hardly such as the toluene equal solvent.

By with these waxes with disperseing such as polyeletrolytes such as ionic surfactant, polymeric acid or polymerization alkali, this dispersion liquid is heated under the temperature that is higher than the wax fusing point and extrude dispersion machine (trade name: GAULIN HOMOGENIZER by homogenizer or high pressure, make by APV Gaulin) disperse under disperse state with high shear force, make the dispersion liquid that contains have an appointment 1 micron or littler particle.

With respect to the total amount of solid constituent in the toner, the addition of releasing agent is preferably 5 weight %～25 weight %, to guarantee in no oily molten system the releasability of photographic fixing image.

Can use such as laser diffraction granularity analyzer (trade name: above-mentioned LA-920) measure releasing agent particle grain size in the dispersion liquid.If used releasing agent, then consider suitable electrostatic property and the permanance that to guarantee particle, preferably at first make resin particle, coloring agent particle and releasing agent particle aggregation, further add resin dispersion liquid then so that make resin particle be attached to the surface of aggregated particle.

Cumulative volume mean diameter D by the toner of making according to the manufacture method of electrostatic image-developing toner of the present invention ₅₀Scope be about 3.0 microns～9.0 microns, be preferably 3.0 microns～5.0 microns.D when toner ₅₀During less than 3.0 microns, can cause the increase of bounding force, cause the deterioration of printing efficiency thus.D when toner ₅₀During greater than 9.0 microns, can cause the deterioration of image resolution ratio.

The volume average particle size profile exponent (GSDv) of resulting toner preferably is about 1.30 or littler.When the GSDv of toner greater than about 1.30 the time, can cause the deterioration of resolution and cause the scattering of toner and such as image deflects such as high background stains.

In order to measure cumulative volume mean diameter D ₅₀And the average particle size distribution index, by for example by coulter counter TAII (Beckmann Coulter manufacturing) or Multisizer II ^TM(BeckmannCoulter manufacturing) measured, and utilizes according to the particle size range (passage) of dividing based on size distribution and the volume and the number of the toner-particle of classification are drawn cumulative distribution curve from smaller side; With semi-invariant is that 16% o'clock particle diameter is defined as D _16vAnd D _16p, be that 50% o'clock particle diameter is defined as D with semi-invariant _50vAnd D _50p, be that 84% o'clock particle diameter is defined as D with semi-invariant _84vAnd D _84pVolume average particle size profile exponent (GSDv) is by (D _84v/ D _16v) ^1/2Calculate, quantity average particle size distribution index (GSDp) is by (D _84p/ D _16p) ^1/2Calculate.

Consider imaging character, the shape coefficient SF1 of resulting toner is about 100～140, is preferably 110～135.Shape coefficient SF1 determines in the following manner: the optical microscopic image that will spread over the toner-particle on the microslide is inserted in the Luzex image analyzer by video camera; Measurement is more than or equal to the girth (ML) and the projected area (A) of 50 toner-particles; Will be by ML ²/ A (=girth ²/ projected area) value defined that calculates is shape coefficient SF1.

For reaching the purpose that provides mobile and improve cleanablity; use the mode similar to carry out drying resulting toner, under drying regime, under shearing force, add then such as particles of inorganic material such as silica, aluminium oxide, titanium dioxide or lime carbonate or such as resin particles such as vinylite particle, polyester granulate or silicone particles to using toner always.

When in aqueous medium with inorganic particle attached to toner surface on when providing mobile and improving cleanablity, the example of inorganic particle comprise all be generally used for toner surface such as external application adjuvants such as silica, aluminium oxide, titanium dioxide, lime carbonate, magnesium carbonate or tricalcium phosphates, and inorganic particle can use under disperse state with ionic surfactant, polymeric acid or polymerization alkali.

The toner that the electrostatic image-developing toner manufacture method according to the invention described above can be made is as electrostatic developer.This developer is not particularly limited,, and can has any composition according to its application purpose as long as it contains with good grounds electrostatic image-developing toner of the present invention.When independent use, this electrostatic image-developing toner is prepared as single composition electrostatic image toner, and when using, then prepare as two composition electrostatic charge image developers with carrier combinations.

In addition, this electrostatic charge image developer (electrostatic image-developing toner) can be used in the imaging process of common electrostatic image development method (xerography).Particularly, imaging process according to the present invention comprises that for example, electrostatic latent image forms technology, toner imaging process, transfer printing process and cleaning procedure.Each technology all is conventional process, and is described in for example JP-A-56-40868 and 49-91231 and other patents.Can be according to imaging method of the present invention by conventionally known finishing such as imaging devices such as duplicating machine or facsimile recorders.It is the technology that forms electrostatic latent image on electrostatic latent image carrier that electrostatic latent image forms technology.The toner imaging process is with latent electrostatic image developing and forms the technology of toner image by the development layer on the developer carrier.The layer that develops is not particularly limited, as long as it contains with good grounds electrostatic charge image developer of the present invention, this developer contains with good grounds electrostatic image-developing toner of the present invention.Transfer printing process is that toner image is transferred to technology on the transfer article.Cleaning procedure is the technology of removing electrostatic charge image developer residual on the electrostatic latent image carrier.In imaging process according to the present invention, preferably also comprise the implementation of processes mode that reclaims.Reclaiming technology is that the image developing toner that will be reclaimed in cleaning procedure is added back on the layer that develops.Can on such as toners such as duplicating machine or facsimile recorder recovery imaging device, implement according to the imaging method that reclaims technology comprising of present embodiment.Imaging method can also be applied to there is not cleaning procedure and reclaim the recovery system of toner in developing process.

Special optimal way of the present invention is listed in hereinafter, but should be appreciated that the present invention is not limited to following embodiment.

(1) a kind of particulate resin dispersion that is used to contain the electrostatic image-developing toner of condensation resin particle, but wherein said condensation resin particle prepare by polycondensation monomer polycondensation in aqueous medium, and have about 0.05 micron～about 2.0 microns median particle diameter.

(2) as (1) described particulate resin dispersion, wherein said resin particle is a crystal type, and its crystalline melting point is about 50 ℃～120 ℃.

(3) as (1) described particulate resin dispersion, wherein said condensation resin particle is a non-crystalline type, and its glass transition temperature is about 50 ℃～80 ℃.

(4) as (1) described particulate resin dispersion, but wherein said polycondensation monomer contains polybasic carboxylic acid and polyvalent alcohol at least.

(5) as (1) described particulate resin dispersion, but wherein said polycondensation monomer carries out polycondensation reaction in the presence of as the acid with surfactant properties of polycondensation catalyst.

(6) as (1) described particulate resin dispersion, but wherein polycondensation monomer carries out polycondensation reaction in the presence of as the catalyzer that contains rare earth metal of polycondensation catalyst.

(7) as (1) described particulate resin dispersion, but wherein polycondensation monomer carries out polycondensation reaction in the presence of as the hydrolytic enzyme of polycondensation catalyst.

(8) as (1) described particulate resin dispersion, wherein said median particle diameter is about 0.1 micron～1.5 microns.

(9) as (1) described particulate resin dispersion, wherein said median particle diameter is about 0.1 micron～1.0 microns.

(10) as (1) described particulate resin dispersion, wherein with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter is less than or equal to the weight ratio of about 0.03 micron condensation resin particle for being less than or equal to about 10%, with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter more than or equal to the weight ratio of about 5.0 microns condensation resin particle for being less than or equal to about 10%.

(11) as (1) described particulate resin dispersion, wherein with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter is less than or equal to the weight ratio of about 0.03 micron condensation resin particle for being less than or equal to about 5%, with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter more than or equal to the weight ratio of about 5.0 microns condensation resin particle for being less than or equal to about 5%.

(12) a kind of manufacture method of electrostatic image-developing toner, this method comprises:

But the polycondensation polycondensation monomer is to obtain the condensation resin particle dispersion in aqueous medium;

Assemble condensation resin particle in the described particulate resin dispersion to obtain aggregated particle; With

By heat-setting aggregated particle,

Wherein said condensation resin particle has about 0.05 micron～about 2.0 microns median particle diameter.

(13) as the manufacture method of (12) described electrostatic image-developing toner, described method also comprises:

In aqueous medium, but described polycondensation monomer is carried out first emulsification or disperse to obtain emulsified dispersed liquid; With

Described emulsified dispersed liquid is carried out second emulsification or disperses to obtain the particulate emulsified dispersed liquid.

(14) as the manufacture method of (13) described electrostatic image-developing toner, wherein at first but polycondensation monomer is mixed with adjuvant and fusion to obtain oily solution, then with described oily solution emulsification or be dispersed in the aqueous medium to obtain described emulsified dispersed liquid.

(15) as the manufacture method of (14) described electrostatic image-developing toner, wherein with described oily solution emulsification or be dispersed in pre-heated aqueous medium to obtain emulsified dispersed liquid.

(16) as the manufacture method of (14) described electrostatic image-developing toner, wherein with described oily solution with solvent emulsification or be dispersed in the aqueous medium with obtain described emulsified dispersed liquid and

Wherein this method also comprises by stirring and heating described particulate emulsified dispersed liquid to remove the solvent in the described particulate emulsified dispersed liquid.

(17) as the manufacture method of (14) described electrostatic image-developing toner,

Wherein by in described oily solution, adding gradually, with described oily solution emulsification or be dispersed in the aqueous medium to obtain emulsified dispersed liquid through pre-heated aqueous medium and by further interpolation aqueous medium with optionally add surfactant and carry out inversion of phases emulsification.

(18) a kind of by the prepared electrostatic image-developing toner of electrostatic image-developing toner manufacture method, this method comprises:

But the polycondensation polycondensation monomer is to obtain the condensation resin particle dispersion in aqueous medium;

Assemble condensation resin particle in the described condensation resin particle dispersion to obtain aggregated particle; With

By heat-setting aggregated particle,

Wherein said condensation resin particle has about 0.05 micron～about 2.0 microns median particle diameter.

(19) as (18) described electrostatic image-developing toner, the cumulative volume mean diameter of wherein said electrostatic image-developing toner is about 3.0 microns～5.0 microns.

(20) a kind of condensation compound particle dispersion that is used to contain the electrostatic image-developing toner of condensation compound particle, but wherein said condensation compound particle prepares by the dehydrating condensation of condensation compound in aqueous medium, and has and be about 0.05 micron～2.0 microns median particle diameter.

(21) as (20) described condensation compound particle dispersion, wherein said condensation compound particle is a crystal type, and its crystalline melting point is about 50 ℃～120 ℃.

(22) as (20) described condensation compound particle dispersion, but wherein said condensation compound contains polybasic carboxylic acid and polyvalent alcohol at least.

(23) as (20) described condensation compound particle dispersion, but wherein said condensation compound carries out dehydration condensation in the presence of as the acid with surfactant properties of dehydrating condensation catalyzer.

(24) as (20) described condensation compound particle dispersion, but wherein said condensation compound carries out dehydration condensation in the presence of as the catalyzer that contains rare earth metal of dehydrating condensation catalyzer.

(25) as (20) described condensation compound particle dispersion, but wherein said condensation compound carries out dehydration condensation in the presence of as the hydrolytic enzyme of dehydrating condensation catalyzer.

(26) as (20) described condensation compound particle dispersion, wherein said median particle diameter is about 0.1 micron～1.5 microns.

(27) as (20) described condensation compound particle dispersion, wherein said median particle diameter is about 0.1 micron～1.0 microns.

(28) as (20) described condensation compound particle dispersion, wherein with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter is less than or equal to the weight ratio of about 0.03 micron condensation compound particle for being less than or equal to about 10%, with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter more than or equal to the weight ratio of about 5.0 microns condensation compound particle for being less than or equal to about 10%.

(29) as (20) described condensation compound particle dispersion, wherein with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter is less than or equal to the weight ratio of about 0.03 micron condensation compound particle for being less than or equal to about 5%, with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter more than or equal to the weight ratio of about 5.0 microns condensation compound particle for being less than or equal to about 5%.

(30) a kind of manufacture method of electrostatic image-developing toner, this method comprises:

Dispersion resin is to obtain particulate resin dispersion in aqueous medium;

In aqueous medium, disperse condensation compound to obtain the condensation compound particle dispersion;

Described particulate resin dispersion is mixed to obtain mixed dispersion liquid with described condensation compound particle dispersion, assemble resin particle in the described mixed dispersion liquid and condensation compound particle to obtain aggregated particle; With

By the described aggregated particle of heat-setting,

But wherein said condensation compound particle dispersion prepares by the dehydrating condensation of condensation compound in aqueous medium, and has and be about 0.05 micron～2.0 microns median particle diameter.

(31) as the manufacture method of (30) described electrostatic image-developing toner, described method also comprises:

In aqueous medium, but described condensation compound is carried out first emulsification or disperse to obtain emulsified dispersed liquid; With

Described emulsified dispersed liquid is carried out second emulsification or disperses to obtain the particulate emulsified dispersed liquid.

(32) as the manufacture method of (31) described electrostatic image-developing toner, but wherein at first condensation compound is mixed with adjuvant and fusion to obtain oily solution, then with described oily solution emulsification and be dispersed in the aqueous medium to obtain emulsified dispersed liquid.

(33) as the manufacture method of (32) described electrostatic image-developing toner, wherein with described oily solution with mix mutually to obtain described emulsified dispersed liquid through pre-heated aqueous medium.

(34) as the manufacture method of (32) described electrostatic image-developing toner, wherein said oily solution with solvent emulsification or be dispersed in aqueous medium with obtain described emulsified dispersed liquid and

Wherein this method also comprises by stirring and heating described particulate emulsified dispersed liquid to remove the solvent in the described particulate emulsified dispersed liquid.

(35) as the manufacture method of (32) described electrostatic image-developing toner,

By in described oily solution, adding gradually, with described oily solution emulsification or be dispersed in the aqueous medium to obtain emulsified dispersed liquid through pre-heated aqueous medium and by further interpolation aqueous medium with optionally add surfactant and carry out inversion of phases emulsification.

(36) a kind of by the prepared electrostatic image-developing toner of electrostatic image-developing toner manufacture method, this method comprises:

Dispersion resin is to obtain particulate resin dispersion in aqueous medium;

In aqueous medium, disperse condensation compound to obtain the condensation compound particle dispersion;

Described particulate resin dispersion is mixed to obtain mixed dispersion liquid with described condensation compound particle dispersion, assemble resin particle in the described mixed dispersion liquid and condensation compound particle to obtain aggregated particle; With

By the described aggregated particle of heat-setting,

But wherein said condensation compound particle dispersion prepares by the dehydrating condensation of condensation compound in aqueous medium, and has and be about 0.05 micron～2.0 microns median particle diameter.

(37) as (36) described electrostatic image-developing toner, the cumulative volume mean diameter of wherein said electrostatic image-developing toner is about 3.0 microns～5.0 microns.

Embodiment

Below, reference example is described in detail the present invention, but the present invention is not limited to the following example.

In the following embodiments, prepare following particle dispersion, coloring agent particle dispersion liquid and releasing agent particle dispersion respectively.Aggregated particle comes in the ionic ground by the polymkeric substance that these dispersion liquids is stirred with the potpourri of certain ratio and add slaine and particle prepares.In particle, add inorganic hydroxide then and be adjusted to neutrality from faintly acid, and it is condensed by glass transition temperature or the higher temperature that is heated to this resin particle with pH with system.After above-mentioned reaction finishes, fully wash, solid-liquid separates and dry to obtain the target toner.Below, will the manufacture method of each dispersion liquid be described.

The preparation of particulate resin dispersion 1-(1)

Dodecylbenzene sulfonic acid: 36 weight portions

1,9-nonanediol: 80 weight portions

1,10-decamethylene dicarboxylic acid: 115 weight portions

Ion exchange water: 1000 weight portions

At first, with the dodecylbenzene sulfonic acid in the above-mentioned composition, 1,9-nonanediol and 1,10-decamethylene dicarboxylic acid mix and be heated to about 120 ℃ so that its fusion and obtain oily solution.This oily solution poured into be heated in advance in about 95 ℃ ion exchange water, by using homogenizer (ULTRA-

T50, by

Works, Inc. makes) with about 5 minutes of gained potpourri emulsification immediately.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this way, can make the vibrin dispersion liquid 1-(1) of crystal type, its mean grain size (median particle diameter) is about 400 nanometers, and fusing point is about 70 ℃, and weight-average molecular weight is about 5500, and solid content is about 18%.

For the particle among the particulate resin dispersion 1-(1), median particle diameter is less than or equal to about 0.03 micron or be about 1.2% more than or equal to the weight of about 5.0 microns particle with respect to the ratio of the general assembly (TW) of particle in the particulate resin dispersion (hereinafter referred to as " larger particles and than the ratio of granule with respect to all particles ").

The preparation of particulate resin dispersion 1-(2)

Dodecylbenzene sulfonic acid: 36 weight portions

1,6-hexanediol: 59 weight portions

Decanedioic acid: 101 weight portions

Ion exchange water: 1000 weight portions

At first, with the dodecylbenzene sulfonic acid in the above-mentioned composition, 1,6-hexanediol and decanedioic acid mix, and by making its fusion to obtain oily solution for extremely about 140 ℃ mixture heated.This oily solution poured into be heated in advance in about 95 ℃ ion exchange water, by using homogenizer (above-mentioned ULTRA-

T50), then,, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours further about 5 minutes of the emulsification in ultrasonic bath of this emulsion with about 5 minutes of gained potpourri emulsification immediately.

In this way, can make the vibrin dispersion liquid 1-(2) of crystal type, its mean grain size (median particle diameter) is about 720 nanometers, and fusing point is about 69 ℃, and weight-average molecular weight is about 4500, and solid content is about 16%.

In particulate resin dispersion 1-(2), larger particles and be about 4.4% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 1-(3)

Dodecyl sulphate: 30 weight portions

1,9-nonanediol: 80 weight portions

Azelaic acid: 94 weight portions

Ion exchange water: 1000 weight portions

At first, with the dodecylbenzene sulfonic acid in the above-mentioned composition, 1,9-nonanediol and decanedioic acid mix, and by making its fusion to obtain oily solution for extremely about 110 ℃ mixture heated.This oily solution poured into be heated in advance in about 95 ℃ ion exchange water, by using homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained potpourri emulsification immediately.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this way, can make the vibrin dispersion liquid 1-(3) of crystal type, its mean grain size (median particle diameter) is about 220 nanometers, and fusing point is about 55 ℃, and weight-average molecular weight is about 7500, and solid content is about 17%.

In particulate resin dispersion 1-(3), larger particles and be about 0.5% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 1-(4)

Cumene sulfonic acid: 25 weight portions

Terephthalic acid (TPA): 46 weight portions

Polyoxyethylene groups (2,4)-2,2-two (4-hydroxy phenyl) propane: 34 weight portions

Ethylene glycol: 20 weight portions

Ion exchange water: 500 weight portions

With cumene sulfonic acid, terephthalic acid (TPA) and the polyoxyethylene groups (2,4)-2 in the above-mentioned composition, 2-two (4-hydroxy phenyl) propane and ethylene glycol mix, and by making its fusion to obtain oily solution for extremely about 110 ℃ mixture heated.This oily solution poured into be heated in advance in about 95 ℃ ion exchange water, and by using homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained potpourri emulsification immediately.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 90 ℃ flask about 20 hours.

In this way, can make the vibrin dispersion liquid 1-(4) of non-crystalline type, its mean grain size (median particle diameter) is about 520 nanometers, and glass transition temperature is about 55 ℃, and weight-average molecular weight is about 4500, and solid content is about 14%.

In particulate resin dispersion 1-(4), larger particles and be about 2.3% with respect to the ratio of all particles than granule.

By using rare-earth metal catalyst to prepare particulate resin dispersion 1-(5)

Dodecylbenzene sulfonic acid scandium (catalyzer that contains rare earth metal): 36 weight portions

1,9-nonanediol: 80 weight portions

1,10-decamethylene dicarboxylic acid: 115 weight portions

Ion exchange water: 1000 weight portions

With the dodecylbenzene sulfonic acid scandium in the above-mentioned composition (catalyzer that contains rare earth metal), 1,9-nonanediol and 1,10-decamethylene dicarboxylic acid mixes, and by making its fusion to obtain oily solution for extremely about 120 ℃ mixture heated.This oily solution poured into be heated in advance in about 95 ℃ ion exchange water, and by using homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained potpourri emulsification immediately.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 80 ℃ flask about 15 hours.

In this way, can make the vibrin dispersion liquid 1-(5) of crystal type, its mean grain size (median particle diameter) is about 370 nanometers, and fusing point is about 70 ℃, and weight-average molecular weight is about 4900, and solid content is about 18%.

In particulate resin dispersion 1-(5), larger particles and be about 1.8% with respect to the ratio of all particles than granule.

By using enzyme catalyst to prepare particulate resin dispersion 1-(6)

Dodecylbenzene sulfonic acid: 12 weight portions

Lipase (enzyme catalyst that the pseudomonad kind is derived): 50 weight portions

1,9-nonanediol: 80 weight portions

1,10-decamethylene dicarboxylic acid: 115 weight portions

Ion exchange water: 1000 weight portions

At first, with the dodecylbenzene sulfonic acid in the above-mentioned composition, lipase, 1,9-nonanediol, and 1,10-decamethylene dicarboxylic acid mixes, and by making its fusion to obtain oily solution to about 120 ℃ mixture heated.This oily solution poured into be heated in advance in about 85 ℃ ion exchange water, and by using homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained potpourri emulsification immediately.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 80 ℃ flask about 15 hours.

In this way, can make the vibrin dispersion liquid 1-(6) of crystal type, its mean grain size (median particle diameter) is about 1070 nanometers, and fusing point is about 69 ℃, and weight-average molecular weight is about 4500, and solid content is about 20%.

In particulate resin dispersion 1-(6), larger particles and be about 8.8% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 1-(7): comparative example

Dodecylbenzene sulfonic acid: 18 weight portions

1,9-nonanediol: 80 weight portions

1,10-decamethylene dicarboxylic acid: 115 weight portions

Ion exchange water: 1000 weight portions

At first, with 1 in the above-mentioned composition, 9-nonanediol and 1,10-decamethylene dicarboxylic acid mix and by with mixture heated to about 120 ℃ and fusion.The solution that so obtains is poured in the ion exchange water that contains dodecylbenzene sulfonic acid under the room temperature.Then, by using homogenizer (above-mentioned ULTRA-

T50) with about 1 minute of gained emulsifying mixture.When stirring, this emulsion was preserved in about 60 ℃ flask about 15 hours.

In this way, can make the vibrin dispersion liquid 1-(7) of crystal type, its mean grain size (median particle diameter) is about 2100 nanometers, and fusing point is about 69 ℃, and weight-average molecular weight is about 3500, and solid content is about 18%.

In particulate resin dispersion 1-(7), larger particles and be about 10.8% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 1-(8): comparative example

Dodecylbenzene sulfonic acid: 36 weight portions

1,4-butylene glycol: 45 weight portions

Azelaic acid: 94 weight portions

Ion exchange water: 1000 weight portions

With the azelaic acid in the above-mentioned composition and 1, the 4-butylene glycol mix and by with mixture heated to about 110 ℃ and fusion.Then, the solution that obtains is thus poured into be heated in advance in about 95 ℃ ion exchange water that contains dodecylbenzene sulfonic acid.Then, by using homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Then, with further about 30 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this way, can make the vibrin dispersion liquid 1-(8) of crystal type, its mean grain size (median particle diameter) is about 25 nanometers, and fusing point is about 48 ℃, and weight-average molecular weight is about 6500, and solid content is about 15%.

In particulate resin dispersion 1-(8), larger particles and be about 12% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 1-(9): non-crystalline type vinylite latex

Styrene: 460 weight portions

N-butyl acrylate: 140 weight portions

Acrylic acid: 12 weight portions

Dodecanediol: 9 weight portions

Each composition in the above-mentioned composition mixed and dissolving so that solution to be provided.Anionic surfactant (DOWFAX with 12 weight portions ^TM, Dow Chemical Company produces) be dissolved in individually in the ion exchange water of 250 weight portions, and above-mentioned solution is added to wherein to obtain potpourri.This potpourri is disperseed in flask and emulsification (monomer emulsion A).In addition, will be by the same anionic surfactant of 1 weight portion (above-mentioned DOWFAX ^TM) formed solution places the flask of polyreaction in the ion exchange water of about 555 weight portions.Subsequently this polyreaction flask is tightly sealed, in water-bath, be heated to about 75 ℃ gradually, and under same temperature, preserve, feed nitrogen simultaneously and under refluxing, this solution is slowly stirred.

To be dissolved in about 20 minutes by constant volume amount charging pump that formed solution dropwise is added in the polyreaction flask in the ion exchange water of about 43 weight portions by the ammonium persulfate of about 9 weight portions, monomer emulsion A also dropwise be added in 200 minutes by constant volume amount charging pump then.

Then, potpourri was kept in about 75 ℃ polyreaction flask simultaneously slowly stir about 3 hours, to finish polyreaction.

In this way, can make resin anion (R.A.) particle dispersion 1-(9), its mean grain size (median particle diameter) is about 210 nanometers, and glass transition temperature is about 53.5 ℃, and weight-average molecular weight is about 31000, and solid content is about 42%.

In particulate resin dispersion 1-(9), larger particles and be about 0.2% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 1-(10)

The dibutyltin oxide of about 0.05 mole of % is added to by 1 of about 40 weight portions, and 1 of 9-nonanediol and 57.5 weight portions are in the formed potpourri of 10-decamethylene dicarboxylic acid.Thereby with the potpourri that obtains thus in the flask of being furnished with emulsification or distribution blade, stir and be heated to about 200 ℃ under reduced pressure to make polyreaction carry out making the crystal type vibrin in 6 hours, the weight-average molecular weight of this resin is about 6200, fusing point is about 69 ℃.About 460g ion exchange water that will contain the 3.2g neopelex of having an appointment is added in the resin of about 80g.The potpourri that so obtains is heated to about 140 ℃ uses homogenizer (above-mentioned ULTRA-simultaneously in the stainless steel flask under pressure

T50) about 1 hour of emulsification is to obtain crystal type polyester resin particle dispersion liquid.

In this way, can make particulate resin dispersion 1-(10), its mean grain size (median particle diameter) is about 450 nanometers, and fusing point is about 69 ℃, and solid content is about 15%.

In particulate resin dispersion 1-(10), larger particles and be about 4.5% with respect to the ratio of all particles than granule.

The preparation of coloring agent particle dispersion liquid 1-(1)

Yellow uitramarine (trade name: Y74, Dainichiseika Color﹠amp; Chemicals Mfg.Co., Ltd produces): 50 weight portions

Anionic surfactant (trade name: NEOGEN R, Daiichi Kogyo Seiyaku Co., Ltd produces): 5 weight portions

Ion exchange water: 200 weight portions

Mixed and the dissolving with each composition in the above-mentioned composition, and with homogenizer (above-mentioned ULTRA-

T50) disperseed about 5 minutes, disperseed about 10 minutes with ultrasonic bath then, mean diameter (median particle diameter) is about 240 nanometers and solid content is about 21.5% yellow particle dispersion liquid 1-(1) to obtain.

The preparation of coloring agent particle dispersion liquid 1-(2)

Except using green pigment (trade name: copper phthalocyanine B15:3, Dainichiseika Color ﹠amp; Chemicals Mfg.Co., Ltd produces) replace in the preparation of coloring agent particle dispersion liquid 1-(1) outside the employed yellow uitramarine, use the mode similar to prepare that mean diameter (median particle diameter) is about 190 nanometers and solid content is about 21.5% cyan colorant particle dispersion 1-(2) to preparing coloring agent particle dispersion liquid 1-(1).

The preparation of coloring agent particle dispersion liquid 1-(3)

Except with magenta pigment (trade name: PR122, Dainippon Ink and Chemicals, Inc. produce) replace in the preparation of coloring agent particle dispersion liquid 1-(1) outside the employed yellow uitramarine, use the mode similar to prepare that mean diameter (median particle diameter) is about 165 nanometers and solid content is about 21.5% coloring agent particle dispersion liquid 1-(3) to preparing coloring agent particle dispersion liquid 1-(1).

The preparation of coloring agent particle dispersion liquid 1-(4)

Except with black pigment (trade name: carbon black, Cabot Corporation. produces) replace in the preparation of coloring agent particle dispersion liquid 1-(1) outside the employed yellow uitramarine, use the mode similar to prepare that mean diameter (median particle diameter) is about 170 nanometers and solid content is about 21.5% coloring agent particle dispersion liquid 1-(4) to preparing coloring agent particle dispersion liquid 1-(1).

The preparation of releasing agent particle dispersion

Paraffin (Ltd. produces, fusing point: 70 ℃ for trade name: HNP 9, Nippon Seiro Co.): 50 weight portions

Anionic surfactant (above-mentioned DOWFAX ^TM): 5 weight portions

Ion exchange water: 200 weight portions

Each mixture of ingredients in the above-mentioned composition is heated to about 95 ℃ also uses homogenizer (ULTRA-

T50,

Works, Inc. produce) thoroughly disperse, and extrude homogenizer (trade name: GAULIN homogenizer, APV Gaulin produces) with high pressure again and disperse that mean diameter (median particle diameter) is about 180 nanometers and solid content is about 21.5% releasing agent particle dispersion to obtain.

Toner embodiment 1-1

The preparation of toner-particle

Particulate resin dispersion 1-(1): 233 weight portions (resin: 42 weight portions)

Particulate resin dispersion 1-(9): 50 weight portions (resin: 21 weight portions)

Coloring agent particle dispersion liquid 1-(1): 40 weight portions (pigment: 8.6 weight portions)

Releasing agent particle dispersion: 40 weight portions (releasing agent: 8.6 weight portions)

Polyaluminium chloride: 0.15 weight portion

Ion exchange water: 300 weight portions

With homogenizer (above-mentioned ULTRA- T50) in circular stainless steel flask with above-mentioned composition in the potpourri of each composition (except particulate resin dispersion 1-(9)) thoroughly disperse, be heated to about 42 ℃ and when stirring, in heated oil bath, it was preserved about 60 minutes then under same temperature; Then, to the particulate resin dispersion 1-(9) that wherein adds about 50 weight portions (resin: about 21 weight portions), and stir this potpourri lenitively.

Sodium hydrate aqueous solution by adding 0.5mol/l is adjusted to 6.0 with the pH of potpourri, is heated to about 95 ℃ when stirring.Dropwise add sodium hydrate aqueous solution and with the pH value of regulating potpourri it can not dropped to be less than or equal to approximately 5.5, this pH value can drop to about 5.0 or lower usually in the process of 95 ℃ of heating.

After the reaction, with potpourri cooling and filtration.Also under reduced pressure it is filtered to carry out the solid-liquid separation with the thorough washing leaching cake of ion exchange water by the Nutsche filtrator.Then filter cake is scattered in about 3L ion exchange water once more at about 40 ℃.Dispersion liquid is stirred under the stirring rate of about 300rpm and washed about 15 minutes.The washing that decompression is undertaken by the Nutsche filtrator down and filter and repeat 5 times, then with solid under vacuum dry about 12 hours to obtain toner-particle.

The cumulative volume mean diameter D of the toner-particle of measuring with coulter counter ₅₀Be about 4.6 microns, its volume average particle size profile exponent GSDv is about 1.20.In addition, this toner-particle is that similar white potato shaped and shape coefficient SF1 toner-particle that measure with Luzex observation station is 130.

The potpourri of the toner-particle of about 50 weight portions and the hydrophobicity silica of about 1.2 weight portions (trade name: TS720, Cabot Corporation produces) is mixed in sample grinder to obtain external application adjuvant toner.

Then, mean diameter is about 50 microns and be about 1% polymethylmethacrylate (Soken Chemical ﹠amp by concentration; Engineering Co., Ltd produces) ferrite carrier of bag quilt and external application adjuvant toner be about with the concentration of toner 5% amount with bowl mill stir about 5 minutes to obtain developer.

The evaluation of toner

By using above-mentioned developer and transfer paper (trade name: J Coated Paper, the production of company limited of Fuji-Xerox) printer (trade name: DOCUCENTER COLOR500 of reequiping, the fixing performance of the toner of being assessed under the processing speed of about 180mm/s the production of company limited of Fuji-Xerox) shows, oilless fixing on perfluor alcoxyl (PFA) pipe fixing roller is functional, its minimum fixing temperature (the image contamination result who is tested by the cloth wiping of image measures separately) is more than or equal to about 120 ℃, the abundant photographic fixing of image, and transfer paper does not have any resistance and discharges.The surface gloss of formed image has 65% relatively well approximately under 140 ℃ fixing temperature.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under 200 ℃ fixing temperature.

Estimate the stability of particulate resin dispersion 1-(1) before the preparation of toner by shearing-homogeneous method, that is, this method comprises: about 100g particulate resin dispersion is placed 300ml stainless steel beaker, with homogenizer (above-mentioned ULTRA-

T50) under shearing force in beaker with about 1 minute of this dispersion liquid homogenizing, by 77 microns nylon meshes this particulate resin dispersion is filtered, observe and whether exist aggregation, result not to have aggregation to generate, show that dispersion liquid has stability (A level).

Toner embodiment 1-2

According to the composition shown in the table 1, except replacing particulate resin dispersion 1-(1) among the embodiment 1-1 with particulate resin dispersion 1-(2), becoming about 5.0, use the mode similar to prepare toner-particle to embodiment 1-1 with coloring agent particle dispersion liquid 1-(2) replacement coloring agent particle dispersion liquid 1-(1) and the pH that in being heated to 95 ℃ process, kept.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 4.40 microns, its volume average particle size profile exponent GSDv is about 1.19.Its shape coefficient SF1 is about 124 (microspheroidals).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 115 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.The surface gloss of formed image has 70% relatively well approximately under 150 ℃ fixing temperature.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of particulate resin dispersion 1-(2) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not have aggregation and generates, and shows that dispersion liquid has stability (A level).

Toner embodiment 1-3

According to the composition shown in the table 1, except replacing particulate resin dispersion 1-(1) among the embodiment 1-1 with particulate resin dispersion 1-(3), replacing particulate resin dispersion 1-(9), become 0.12 weight portion, use the mode similar to prepare toner-particle to embodiment 1-1 with the consumption of coloring agent particle dispersion liquid 1-(3) replacement coloring agent particle dispersion liquid 1-(2) and polyaluminium chloride with particulate resin dispersion 1-(4).

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 4.20 microns, its volume average particle size profile exponent GSDv is about 1.22, and its shape coefficient SF1 is about 119 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 100 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.The surface gloss of formed image has 85% relatively well approximately under 150 ℃ fixing temperature.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (A level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of particulate resin dispersion 1-(2) and 1-(3) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not have aggregation and generates, and shows that dispersion liquid has stability (A level).

Toner embodiment 1-4

According to the composition shown in the table 1,, use the mode similar to prepare toner-particle to embodiment 1-1 except replace the particulate resin dispersion 1-(1) among the embodiment 1-1 with particulate resin dispersion 1-(5).

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 3.92 microns, its volume average particle size profile exponent GSDv is about 1.22, and its shape coefficient SF1 is about 135 (white potato shaped).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 110 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.The surface gloss of formed image has 55% relatively well approximately under 150 ℃ fixing temperature.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of particulate resin dispersion 1-(5) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not have aggregation and generates, and shows that dispersion liquid has stability (A level).

Toner embodiment 1-5

According to the composition shown in the table 1, except replacing particulate resin dispersion 1-(2) among the embodiment 1-2 with particulate resin dispersion 6 so that make all particulate resin dispersions be particulate resin dispersion 1-(6), therefore do not use particulate resin dispersion 1-(9) in addition, use the mode similar to prepare toner-particle to embodiment 1-2.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 3.50 microns, its volume average particle size profile exponent GSDv is about 1.25, and its shape coefficient SF1 is about 120 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 90 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.The surface gloss of formed image has 55% relatively well approximately under 150 ℃ fixing temperature.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of particulate resin dispersion 1-(6) before the preparation of toner by aforesaid shearing-homogeneous method, the result has the minor agglomeration may thing to generate but can not cause practical problems, shows that dispersion liquid is approximate to have stability (B level).

Toner comparative example 1-1

According to the composition shown in the table 1, except replace the particulate resin dispersion 1-(2) among the embodiment 1-2 with particulate resin dispersion 1-(7), use the mode similar to prepare toner-particle to embodiment 1-2.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 5.50 microns, its volume average particle size profile exponent GSDv is about 1.30, and its shape coefficient SF1 is about 135 (white potato shaped).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 120 ℃ or higher, the abundant photographic fixing of image.Yet the discharge of transfer paper is bad, causes image fixing curling and coiling of paper afterwards.It is stained to observe heat under about 180 ℃ fixing temperature.In toner, there is coarse particle.In addition, observed such as image deflects such as blank parts (D level).

In addition, estimate the stability of particulate resin dispersion 1-(7) before the preparation of toner by aforesaid shearing-homogeneous method, the result has produced a large amount of aggregation (D level).

Toner comparative example 1-2

According to the composition shown in the table 1, except replace the particulate resin dispersion 1-(2) among the embodiment 1-2 with particulate resin dispersion 1-(8), use the mode similar to prepare toner-particle to embodiment 1-2.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 5.70 microns, its volume average particle size profile exponent GSDv is about 1.26, and its shape coefficient SF1 is about 120 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing performance that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode bad.Its minimum fixing temperature is about 90 ℃ or higher.The abundant photographic fixing of image.Yet the discharge of transfer paper is bad, causes image fixing curling and coiling of paper afterwards.It is stained to observe heat under about 140 ℃ fixing temperature.In addition, observed such as image deflects such as blank parts (D level), thereby this image is unworthy abundant evaluation.

In addition, estimate the stability of particulate resin dispersion 1-(8) before the preparation of toner by aforesaid shearing-homogeneous method, the result has produced some aggregations (C level).

Toner comparative example 1-3

According to the composition shown in the table 1, except replace the particulate resin dispersion 1-(2) among the embodiment 1-2 with particulate resin dispersion 1-(10), use the mode similar to prepare toner-particle to embodiment 1-2.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 5.95 microns, its volume average particle size profile exponent GSDv is about 1.40, and its shape coefficient SF1 is about 118 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 1-1 in similar mode prepare by toner-particle.With to embodiment 1-1 in the oilless fixing performance that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode bad.Its minimum fixing temperature is about 130 ℃ or higher.The abundant photographic fixing of image.Yet the discharge of transfer paper is bad, causes image fixing curling and coiling of paper afterwards.It is stained to observe heat under about 160 ℃ fixing temperature.In addition, observe the defective of solid-state image and dispersing of toner, thereby confirmed this toner bad (D level).

In addition, estimate the stability of particulate resin dispersion 1-(10) before the preparation of toner by aforesaid shearing-homogeneous method, the result has produced a large amount of aggregations, and a large amount of aggregations remain in (D level) on the nylon mesh.

The result of these embodiment and comparative example is summarised in the table 1.In table 1, the stability of particulate resin dispersion is done following evaluation: the A level: do not have any aggregation; B level: the minor agglomeration may thing is arranged and can not cause practical problems; C level: some aggregations are arranged; D level: a large amount of aggregations are arranged.In addition, the evaluation criterion to picture quality is as follows: A level: fabulous; B level: good; D level: image deflects are arranged.

The above results shows can produce the toner of being made by condensation resin effectively, and by as shown in the Examples thereby the median particle diameter of condensation resin particle being adjusted to the fixing performance that particular range improves picture quality and toner significantly, described condensation resin particle is by directly polymerization and emulsification disperse to prepare in aqueous medium.

On the contrary, be understandable that, shown in comparative example, when the median particle diameter of condensation resin particle does not fall in the particular range, although in aqueous medium, disperse to prepare the condensation resin particle by direct polymerization and emulsification, or when manufacturing condensation resin particle is dispersed in the aqueous medium then separately, although in the particular range that the median particle diameter of condensation resin particle drops on, compare with the toner among the embodiment, by the performance degradation of the prepared toner-particle of above-mentioned situation.

The preparation of condensation compound particle dispersion 2-(1)

Dodecylbenzene sulfonic acid: 23 weight portions

Mountain Yu acid: 104 weight portions

Docosyl alcohol: 100 weight portions

Ion exchange water: 816 weight portions

At first, the dodecylbenzene sulfonic acid in the above-mentioned composition, mountain Yu acid and docosyl alcohol are mixed and be heated to about 90 ℃ to obtain oily solution.This oily solution poured into be heated in advance in about 90 ℃ ion exchange water, and by homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this way, can make condensation compound particle dispersion 2-(1), its mean grain size (median particle diameter) is about 220 nanometers, and fusing point is about 69 ℃, and solid content is about 20%.

For the particle among the condensation compound particle dispersion 2-(1), larger particles and be about 0.5% with respect to the ratio of all particles than granule.

The preparation of condensation compound particle dispersion 2-(2)

Dodecylbenzene sulfonic acid: 23 weight portions

Mountain Yu acid: 250 weight portions

Pentaerythrite: 25 weight portions

Ion exchange water: 1100 weight portions

At first, with the dodecylbenzene sulfonic acid in the above-mentioned composition, mountain Yu acid and pentaerythrite mixes and by with mixture heated to about 250 ℃ and fusion to obtain oily solution.This oily solution poured into be heated in advance in about 90 ℃ ion exchange water, and by homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 80 ℃ flask about 15 hours.

In this way, can make condensation compound particle dispersion 2-(2), its mean grain size (median particle diameter) is about 1820 nanometers, and fusing point is about 85 ℃, and solid content is about 20%.

In condensation compound particle dispersion 2-(2), larger particles and be about 8.2% with respect to the ratio of all particles than granule.

The preparation of condensation compound particle dispersion 2-(3)

Dodecylbenzene sulfonic acid: 30 weight portions

Palmitic acid: 188 weight portions

Pentaerythrite: 25 weight portions

Ion exchange water: 852 weight portions

At first, with the dodecylbenzene sulfonic acid in the above-mentioned composition, palmitic acid and pentaerythrite mixes and by with mixture heated to about 250 ℃ and fusion to obtain oily solution.This oily solution poured into be heated in advance in about 90 ℃ ion exchange water, and by homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this way, can make condensation compound particle dispersion 2-(3), its mean grain size (median particle diameter) is about 640 nanometers, and fusing point is about 72 ℃, and solid content is about 20%.

In condensation compound particle dispersion 2-(3), larger particles and be about 1.5% with respect to the ratio of all particles than granule.

The preparation of condensation compound particle dispersion 2-(4)

Cumene sulfonic acid: 30 weight portions

Myristic acid: 188 weight portions

Dipentaerythritol: 25 weight portions

Ion exchange water: 640 weight portions

At first, the cumene sulfonic acid in the above-mentioned composition, myristic acid and dipentaerythritol are mixed and be heated to about 210 ℃ and fusion to obtain oily solution.This oily solution poured into be heated in advance in about 95 ℃ ion exchange water, and by homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 80 ℃ flask about 18 hours.

In this way, can make condensation compound particle dispersion 2-(4), its mean grain size (median particle diameter) is about 420 nanometers, and fusing point is about 68 ℃, and solid content is about 20%.

In condensation compound particle dispersion 2-(4), larger particles and be about 0.9% with respect to the ratio of all particles than granule.

By using rare-earth metal catalyst to prepare condensation compound particle dispersion 2-(5)

Dodecylbenzene sulfonic acid scandium (catalyzer that contains rare earth metal): 40 weight portions

Stearic acid: 105 weight portions

Stearyl alcohol: 100 weight portions

Ion exchange water: 820 weight portions

At first, with the dodecylbenzene sulfonic acid scandium in the above-mentioned composition, stearic acid and stearyl alcohol mixes and by with mixture heated to about 70 ℃ and fusion to obtain oily solution.This oily solution poured into be heated in advance in about 90 ℃ ion exchange water, and by homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Then, with further about 5 minutes of the emulsification in ultrasonic bath of this emulsion, when stirring, this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this way, can make condensation compound particle dispersion 2-(5), its mean grain size (median particle diameter) is about 120 nanometers, and fusing point is about 60 ℃, and solid content is about 20%.

In condensation compound particle dispersion 2-(5), larger particles and be about 6.8% with respect to the ratio of all particles than granule.

By using enzyme catalyst to prepare condensation compound particle dispersion 2-(6)

Dodecylbenzene sulfonic acid: 12 weight portions

Lipase (enzyme catalyst that the pseudomonad kind is derived): 50 weight portions

Palmitic acid: 209 weight portions

Glycerine: 25 weight portions

Ion exchange water: 960 weight portions

At first, the dodecylbenzene sulfonic acid in the above-mentioned composition, lipase (enzyme catalyst that the pseudomonad kind is derived), palmitic acid and glycerine are mixed and be heated to about 70 ℃ and fusion to obtain oily solution.This oily solution poured into be heated in advance in about 90 ℃ ion exchange water, and by homogenizer (above-mentioned ULTRA- T50) with about 5 minutes of gained emulsifying mixture.This emulsion continued emulsification about 5 minutes in ultrasonic bath, when stirring this emulsion was preserved in about 70 ℃ flask about 15 hours.

In this mode, can make condensation compound particle dispersion 2-(6), its mean grain size (median particle diameter) is about 120 nanometers, and fusing point is about 62 ℃, and solid content is about 20%.

In condensation compound particle dispersion 2-(6), larger particles and be about 9.0% with respect to the ratio of all particles than granule.

Preparation condensation compound particle dispersion 2-(7) as a comparative example

Dodecylbenzene sulfonic acid: 23 weight portions

Mountain Yu acid: 250 weight portions

Pentaerythrite: 25 weight portions

Ion exchange water: 1100 weight portions

At first, the mountain Yu in above-mentioned composition acid is mixed with pentaerythrite and pass through mixture heated extremely about 250 ℃ and fusion.Mixed solution is poured in the ion exchange water that is dissolved with dodecylbenzene sulfonic acid in advance in room temperature, and by homogenizer (above-mentioned ULTRA-

T50) with about 5 minutes of gained emulsifying mixture.Ultrasonic bath of no use is carried out further emulsification.When appropriateness stirs, this emulsion was preserved in about 80 ℃ flask about 15 hours.

In this way, can make condensation compound particle dispersion 2-(7), its mean grain size (median particle diameter) is about 2120 nanometers, and fusing point is about 85 ℃, and solid content is about 20%.

In condensation compound particle dispersion 2-(7), larger particles and be about 10.5% with respect to the ratio of all particles than granule.

The preparation of condensation compound particle dispersion 2-(8): comparative example

At first, following condensation compound is placed in the flask that is equipped with thermometer, confession nitrogen pipe, condenser pipe and stirrer.

Mountain Yu acid: 104 weight portions

Docosyl alcohol: 100 weight portions

Then, nitrogen flow down stir this potpourri and be heated to 180 ℃ about 12 hours, under reduced pressure boil off reaction water simultaneously.

Take by weighing the condensation compound that about 180g so obtains.This potpourri is added in the ion exchange water of neopelex that about 900g contains 2 weight % approximately, with this mixture heated to about 80 ℃, with homogenizer (above-mentioned ULTRA-

T50) disperse, add dispersion with nanomizer (Yoshida Kikai Co., Ltd produce) at about 90 ℃.

In this way, can make condensation compound particle dispersion 2-(8), its mean grain size (median particle diameter) is about 820 nanometers, and fusing point is about 69 ℃, and solid content is about 20%.

In addition, in condensation compound particle dispersion 2-(8), larger particles and be about 7.2% with respect to the ratio of all particles than granule.

The preparation of particulate resin dispersion 2-(1): crystal type polyester latex

To contain 1 of the 90.5 moles of % that have an appointment, 1 of the sour composition of the 5-tert-butyl isophthalic acid of the dimethyl isophthalate of 10-dodecanedicarboxylic acid, about 2 moles of %-5-sodium sulfonate and about 7.5 moles of %, about 100 moles of %, 9-nonanediol and catalyzer Ti (OBu) ₄(being about 0.014 weight % with respect to sour composition) places the three-neck flask of oven dry.In decompression and provide under the condition of nitrogen degasification is carried out in the inside of this flask.In inert atmosphere about 180 ℃ this potpourri refluxed under about 6 hours of mechanical raking.Then, remove unnecessary ethylene glycol by distillation under reduced pressure, with this potpourri be heated to gradually 220 ℃ and under same temperature stir about got thickness up to solution becomes in 2 hours.When the weight-average molecular weight of being measured by gel permeation chromatography (GPC) reaches about 11000 the time, stop the distillation under the decompression, potpourri is cooled off, to obtain crystal type polyester 2-(1) in air.

Then, the crystal type polyester 2-(1) of about 80g and the deionized water of about 720g are placed the stainless steel beaker and be heated to about 95 ℃ at heating bath.Begin with homogenizer (above-mentioned ULTRA-from this crystal type vibrin fusion

T50) speed with 8000rpm stirs this crystal type vibrin.Then, along with about 20g contains 1.6g anionic surfactant (trade name: NEOGEN RK, Daiichi Kogyo Seiyaku Co., the dropping of dilute aqueous solution Ltd production), the emulsification of gained resin disperse to provide mean diameter to be about 0.15 micron crystal type vibrin dispersion liquid 2-(1).

The preparation of particulate resin dispersion 2-(2): non-crystalline type vinylite latex

Styrene: 460 weight portions

N-butyl acrylate: 140 weight portions

Acrylic acid: 12 weight portions

Dodecanediol: 9 weight portions

Each composition in the above-mentioned composition mixed and dissolving to obtain solution.Anionic surfactant (above-mentioned DOWFAX with 12 weight portions ^TM) be dissolved in separately in the ion exchange water of 250 weight portions, and above-mentioned solution is added to wherein.The potpourri that obtains is thus disperseed in flask and emulsification (monomer emulsion A).Then, will be by the same anionic surfactant of 1 weight portion (above-mentioned DOWFAX ^TM) formed solution places the flask of polyreaction in the ion exchange water of 555 weight portions.Subsequently this polyreaction flask is tightly sealed, in water-bath, be heated to about 75 ℃ gradually, and under same temperature, preserve, feed nitrogen simultaneously and under refluxing, this solution is relaxed stirring.

To be dissolved in about 20 minutes by constant volume amount charging pump that formed solution dropwise is added in the polyreaction flask in the ion exchange water of about 43 weight portions by the ammonium persulfate of about 9 weight portions.In 200 minutes, dropwise add monomer emulsion A by constant volume amount charging pump then.

Then, potpourri is kept in about 75 ℃ polyreaction flask relaxed stir about simultaneously 3 hours, to finish polyreaction.

In this way, can make non-crystalline type resin dispersion liquid 2-(2), its mean grain size (median particle diameter) is about 210 nanometers, and glass transition temperature is about 53.5 ℃, and weight-average molecular weight is about 31000, and solid content is about 42%.

The preparation of coloring agent particle dispersion liquid 2-(1)

Yellow uitramarine (trade name: Y74, Dainichiseika Color﹠amp; Chemicals Mfg.Co., Ltd produces): 50 weight portions

Anionic surfactant (trade name: above-mentioned NEOGEN R): 5 weight portions

Ion exchange water: 200 weight portions

Mixed and the dissolving with each composition in the above-mentioned composition, and with homogenizer (above-mentioned ULTRA-

T50) disperseed about 5 minutes, disperseed about 10 minutes with ultrasonic bath then, mean diameter (median particle diameter) is about 240 nanometers and solid content is about 21.5% yellow particle dispersion liquid 2-(1) to obtain.

The preparation of coloring agent particle dispersion liquid 2-(2)

Except using green pigment (trade name: copper phthalocyanine B15:3, Dainichiseika Color﹠amp; Chemicals Mfg.Co., Ltd produces) replace in the preparation of coloring agent particle dispersion liquid 2-(1) outside the employed yellow uitramarine, prepare in order to the mode similar that mean diameter (median particle diameter) is about 190 nanometers and solid content is about 21.5% cyan colorant particle dispersion 2-(2) to preparation coloring agent particle dispersion liquid 2-(1).

The preparation of coloring agent particle dispersion liquid 2-(3)

Except with magenta pigment (trade name: PR122, Dainippon Ink and Chemicals, Inc. produce) replace in the preparation of coloring agent particle dispersion liquid 2-(1) outside the employed yellow uitramarine, use the mode similar to prepare that mean diameter (median particle diameter) is about 165 nanometers and solid content is about 21.5% coloring agent particle dispersion liquid 2-(3) to preparing coloring agent particle dispersion liquid 2-(1).

The preparation of coloring agent particle dispersion liquid 2-(4)

Except with black pigment (trade name: carbon black, Cabot Corporation. produces) replace in the preparation of coloring agent particle dispersion liquid 2-(1) outside the employed yellow uitramarine, use the mode similar to prepare that mean diameter (median particle diameter) is about 170 nanometers and solid content is about 21.5% coloring agent particle dispersion liquid 2-(4) to preparing coloring agent particle dispersion liquid 2-(1).

The preparation of releasing agent particle dispersion 2-(1)

Paraffin (Ltd. produces, fusing point: 70 ℃ for trade name: HNP9, Nippon Seiro Co.): 50 weight portions

Anionic surfactant (above-mentioned DOWFAX ^TM): 5 weight portions

Ion exchange water: 200 weight portions

Each mixture of ingredients in the above-mentioned composition is heated to about 95 ℃ also uses homogenizer (above-mentioned ULTRA-

T50) thoroughly disperse, and again with high pressure extrude homogenizer (trade name: the GAULIN homogenizer, as mentioned above) disperse that mean diameter (median particle diameter) is about 180 nanometers and solid content is about 21.5% releasing agent particle dispersion to obtain.

Toner embodiment 2-1

The preparation of toner-particle

Particulate resin dispersion 2-(1): 210 weight portions (resin: 21 weight portions)

Particulate resin dispersion 2-(2): 100 weight portions (resin: 21 weight portions)

Coloring agent particle dispersion liquid 2-(1): 28 weight portions (pigment: 6 weight portions)

Condensation compound particle dispersion 2-(1): 50 weight portions (condensation compound: 10 weight portions)

Polyaluminium chloride: 0.15 weight portion

Ion exchange water: 300 weight portions

With homogenizer (above-mentioned ULTRA-

T50) in circular stainless steel flask with above-mentioned composition in the potpourri of each composition (except particulate resin dispersion 2-(2)) thoroughly disperse, be heated to about 42 ℃ and when stirring, in heated oil bath, it was preserved about 60 minutes then under same temperature; Then, to the particulate resin dispersion 2-(2) that wherein adds about 50 weight portions (resin: about 21 weight portions), and stir this potpourri lentamente.

Sodium hydrate aqueous solution by adding 0.5mol/l is adjusted to 6.0 with the pH of potpourri, is heated to about 95 ℃ when stirring.Dropwise add sodium hydrate aqueous solution and with the pH value of regulating potpourri it can not dropped to be less than or equal to approximately 5.5, this pH value can drop to about 5.0 or lower usually in the process of 95 ℃ of heating.

After the reaction, with potpourri cooling and filtration.Also under reduced pressure it is filtered to carry out the solid-liquid separation with the thorough washing leaching cake of ion exchange water by the Nutsche filtrator.Then filter cake is scattered in about 3L ion exchange water once more at about 40 ℃.Dispersion liquid is stirred under the stirring rate of about 300rpm and washed about 15 minutes.The washing that decompression is undertaken by the Nutsche filtrator down and filter and repeat 5 times, then with solid under vacuum dry about 12 hours to obtain toner-particle.

The cumulative volume mean diameter D of the toner-particle of measuring with coulter counter ₅₀Be about 4.8 microns, its volume average particle size profile exponent GSDv is about 1.22.In addition, this toner-particle is that similar white potato shaped and shape coefficient SF1 toner-particle that measure with Luzex observation station is 129.

The potpourri of the toner-particle of about 50 weight portions and the hydrophobicity silica of about 1.5 weight portions (trade name: TS720, Cabot Corporation produces) is mixed in sample grinder to obtain external application adjuvant toner.

Then, mean diameter is about 50 microns and be about 1% polymethylmethacrylate (Soken Chemical ﹠amp with concentration; Engineering Co., Ltd produces) ferrite carrier of bag quilt and external application adjuvant toner be about with the concentration of toner 5% amount with bowl mill stir about 5 minutes to obtain developer.

The evaluation of toner

By using above-mentioned developer and transfer paper (trade name: J Coated Paper, printer (the trade name: DOCUCENTER COLOR500 of repacking as mentioned above), the fixing performance of the toner of being assessed under the processing speed of about 180mm/s as mentioned above) shows, oilless fixing on PFA pipe fixing roller is functional, its minimum fixing temperature (by the painted independent mensuration of image of testing from the cloth wiping of image) is more than or equal to about 110 ℃, the abundant photographic fixing of image, and transfer paper does not have any resistance and discharges.Developing performance and transfer printing performance are all good.That is, this toner provides the high quality graphic (A level) of the excellence that does not have image deflects.Even it is stained also not observe heat under 200 ℃ fixing temperature.

Estimate the stability of condensation compound particle dispersion 2-(1) before the preparation of toner by shearing-homogeneous method, that is, this method comprises: about 100g particulate resin dispersion is placed 300ml stainless steel beaker, with homogenizer (above-mentioned ULTRA-

T50) under shearing force in beaker with about 1 minute of this dispersion liquid homogenizing, by 77 microns nylon meshes this particulate resin dispersion is filtered, observe and whether exist aggregation, result not to have aggregation to generate, show that dispersion liquid has stability (A level).

Toner embodiment 2-2

Except replacing condensation compound particle dispersion 2-(1) among the embodiment 2-1 with condensation compound particle dispersion 2-(2), becoming about 5.0, use the mode similar to prepare toner-particle to embodiment 2-1 with coloring agent particle dispersion liquid 2-(2) replacement coloring agent particle dispersion liquid 2-(1) and the pH that in being heated to 95 ℃ process, kept.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 4.60 microns, its volume average particle size profile exponent GSDv is about 1.19.Its shape coefficient SF1 is about 123 (microspheroidals).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 110 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.The surface gloss of formed image has 70% relatively well approximately under 150 ℃ fixing temperature.Developing performance and transfer printing performance are also good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of condensation compound particle dispersion 2-(2) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not almost have aggregation and generates, and shows that dispersion liquid has stability (B level).

Toner embodiment 2-3

Except replace with condensation compound particle dispersion 2-(3) condensation compound particle dispersion 2-(1) among the embodiment 2-1, with coloring agent particle dispersion liquid 2-(3) replacement coloring agent particle dispersion liquid 2-(2), the pH that in being heated to 95 ℃ process, kept become about 5.0 and the quantitative change of polyaluminium chloride be 0.12 weight portion, use the mode similar to prepare toner-particle to embodiment 2-1.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 3.90 microns, its volume average particle size profile exponent GSDv is about 1.22.Its shape coefficient SF1 is about 120 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 100 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of condensation compound particle dispersion 2-(2) and 2-(3) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not almost have aggregation and generates, and shows that dispersion liquid has stability (B level).

Toner embodiment 2-4

Except replace the condensation compound particle dispersion 2-(1) among the embodiment 2-1 with condensation compound particle dispersion 2-(4), use the mode similar to prepare toner-particle to embodiment 2-1.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 4.50 microns, its volume average particle size profile exponent GSDv is about 1.22.Its shape coefficient SF1 is about 135 (white potato shaped).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 100 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of condensation compound particle dispersion 2-(4) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not have aggregation and generates, and shows that dispersion liquid has stability (A level).

Toner embodiment 2-5

Except replacing the condensation compound particle dispersion 2-(1) among the embodiment 2-1 and not using particulate resin dispersion 2-(2) with condensation compound particle dispersion 2-(5), so that only use particulate resin dispersion 2-(1), use the mode similar to prepare toner-particle to routine 2-1 as outside the particulate resin dispersion.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 3.50 microns, its volume average particle size profile exponent GSDv is about 1.25.Its shape coefficient SF1 is about 120 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 90 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of condensation compound particle dispersion 2-(5) before the preparation of toner by aforesaid shearing-homogeneous method, the result does not have aggregation and generates, and shows that dispersion liquid has stability (A level).

Toner embodiment 2-6

Except replace the condensation compound particle dispersion 2-(1) among the embodiment 2-1 with condensation compound particle dispersion 2-(6), do not use particulate resin dispersion 2-(1), so that only use particulate resin dispersion 2-(2) as particulate resin dispersion, replace the coloring agent particle dispersion liquid 2-(1) among the embodiment 2-1 and further add outside the releasing agent dispersion liquid of 20 weight portions, use the mode similar to prepare toner-particle to embodiment 2-1 with coloring agent particle dispersion liquid 2-(2).

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 4.90 microns, its volume average particle size profile exponent GSDv is about 1.20, and its shape coefficient SF1 is about 132 (white potato shaped).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 130 ℃ or higher, the abundant photographic fixing of image, transfer paper does not have any resistance and discharges.Developing performance and transfer printing performance are all good.This toner provides the good high quality graphic that does not have image deflects (B level).Even it is stained also not observe heat under about 200 ℃ fixing temperature.

In addition, estimate the stability of condensation compound particle dispersion 2-(6) before the preparation of toner by aforesaid shearing-homogeneous method, the result has the minor agglomeration may thing to generate, and shows that dispersion liquid is approximate to have stability (B level).

Toner comparative example 2-1

Except replace the condensation compound particle dispersion 2-(2) among the embodiment 2-1 with condensation compound particle dispersion 2-(7), use the mode similar to prepare toner-particle to embodiment 2-1.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 5.50 microns, its volume average particle size profile exponent GSDv is about 1.30, and its shape coefficient SF1 is about 135 (white potato shaped).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode functional, its minimum fixing temperature is about 120 ℃ or higher, the abundant photographic fixing of image, yet, the discharge of transfer paper is bad, causes image fixing curling and coiling of paper afterwards.It is stained to observe heat under about 180 ℃ fixing temperature.In toner, there is coarse particle.In addition, observed such as image deflects such as blank parts (D level).

In addition, estimate the stability of condensation compound particle dispersion 2-(7) before the preparation of toner by aforesaid shearing-homogeneous method, the result has produced a large amount of aggregation (D level).

Toner comparative example 2-2

Except replace the condensation compound particle dispersion 2-(1) among the embodiment 2-1 with condensation compound particle dispersion 2-(8), use the mode similar to prepare toner-particle to embodiment 2-1.

The cumulative volume mean diameter D of this gained toner-particle ₅₀Be about 5.8 microns, its volume average particle size profile exponent GSDv is about 1.35, and its shape coefficient SF1 is about 120 (spheries).

Developer is prepared by external application adjuvant toner, described external application adjuvant toner use to embodiment 2-1 in similar mode prepare by toner-particle.With to embodiment 2-1 in the oilless fixing performance that is presented on the PFA pipe fixing roller of the evaluation of fixing performance of the toner that carries out of similar mode bad.In addition, about the evaluation of minimum fixing temperature, the discharge of transfer paper is bad, and it is stained to observe significant heat, thereby this image is unworthy abundant evaluation.In addition, in toner, there is coarse particle, and observed such as image deflects such as blank parts (D level).

In addition, estimate the stability of condensation compound particle dispersion 2-(8) before the preparation of toner by aforesaid shearing-homogeneous method, the result has produced a large amount of aggregation (D level).

The result of these embodiment and comparative example is summarised in the table 2.In table 2, as follows to the evaluation criterion of condensation compound particle dispersion stability: the A level: as not have any aggregation; B level: the minor agglomeration may thing is arranged and can not cause practical problems; C level: some aggregations are arranged; D level: a large amount of aggregations are arranged.In addition, the evaluation criterion to picture quality is as follows: A level: fabulous; B level: good; D level: image deflects are arranged.

The above results shows can produce the toner of being made by condensation compound effectively, and by as shown in the Examples thereby the median particle diameter of condensation compound particle being adjusted to the fixing performance that particular range improves picture quality and toner significantly, described condensation compound particle is by directly condensation and emulsification disperse to prepare in aqueous medium.

On the contrary, be understandable that, shown in comparative example, when the median particle diameter of condensation compound particle does not fall in the particular range, although in aqueous medium, disperse to prepare the condensation compound particle by direct condensation and emulsification, or when manufacturing condensation compound particle is dispersed in the aqueous medium then separately, although in the particular range that the median particle diameter of condensation compound particle drops on, compare with the toner among the embodiment, by performance (such as picture quality and the fixing performance) deterioration of the prepared toner-particle of above-mentioned situation.

Claims (35)

1. particulate resin dispersion that is used to contain the electrostatic image-developing toner of condensation resin particle, but wherein said condensation resin particle is prepared by polycondensation monomer polycondensation in aqueous medium, and have 0.05 micron～2.0 microns median particle diameter, but wherein said polycondensation monomer contains polybasic carboxylic acid and polyvalent alcohol at least.

2. particulate resin dispersion as claimed in claim 1, wherein said condensation resin particle is a crystal type, and its crystalline melting point is 50 ℃～120 ℃.

3. particulate resin dispersion as claimed in claim 1, wherein said condensation resin particle is a non-crystalline type, and its glass transition temperature is 50 ℃～80 ℃.

4. particulate resin dispersion as claimed in claim 1, but wherein said polycondensation monomer carries out polycondensation reaction in the presence of as the acid with surfactant properties of polycondensation catalyst.

5. particulate resin dispersion as claimed in claim 1, but wherein polycondensation monomer carries out polycondensation reaction in the presence of as the catalyzer that contains rare earth metal of polycondensation catalyst.

6. particulate resin dispersion as claimed in claim 1, but wherein polycondensation monomer carries out polycondensation reaction in the presence of as the hydrolytic enzyme of polycondensation catalyst.

7. particulate resin dispersion as claimed in claim 1, wherein said median particle diameter are 0.1 micron～1.5 microns.

8. particulate resin dispersion as claimed in claim 1, wherein said median particle diameter are 0.1 micron～1.0 microns.

9. particulate resin dispersion as claimed in claim 1, wherein with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter is less than or equal to 0.03 micron the weight ratio of condensation resin particle for being less than or equal to 10%, with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter more than or equal to the weight ratio of 5.0 microns condensation resin particle for being less than or equal to 10%.

10. particulate resin dispersion as claimed in claim 1, wherein with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter is less than or equal to 0.03 micron the weight ratio of condensation resin particle for being less than or equal to 5%, with respect to the general assembly (TW) of described condensation resin particle, described median particle diameter more than or equal to the weight ratio of 5.0 microns condensation resin particle for being less than or equal to 5%.

11. the manufacture method of an electrostatic image-developing toner, this method comprises:

But the polycondensation polycondensation monomer to be obtaining the condensation resin particle dispersion in aqueous medium, but wherein said polycondensation monomer contains polybasic carboxylic acid and polyvalent alcohol at least;

Assemble condensation resin particle in the described particulate resin dispersion to obtain aggregated particle; With

By heat-setting aggregated particle,

Wherein said condensation resin particle has 0.05 micron～2.0 microns median particle diameter.

12. the manufacture method of electrostatic image-developing toner as claimed in claim 11, described method also comprises:

In aqueous medium, but described polycondensation monomer is carried out first emulsification or disperse to obtain emulsified dispersed liquid; With

Described emulsified dispersed liquid is carried out second emulsification or disperses to obtain the particulate emulsified dispersed liquid.

13. the manufacture method of electrostatic image-developing toner as claimed in claim 12, wherein at first but polycondensation monomer is mixed with adjuvant and fusion to obtain oily solution, then with described oily solution emulsification or be dispersed in the aqueous medium to obtain described emulsified dispersed liquid.

14. the manufacture method of electrostatic image-developing toner as claimed in claim 13 is wherein with described oily solution emulsification or be dispersed in pre-heated aqueous medium to obtain emulsified dispersed liquid.

15. the manufacture method of electrostatic image-developing toner as claimed in claim 13, wherein with described oily solution with solvent emulsification or be dispersed in the aqueous medium with obtain described emulsified dispersed liquid and

Wherein this method also comprises by stirring and heating described particulate emulsified dispersed liquid to remove the solvent in the described particulate emulsified dispersed liquid.

16. the manufacture method of electrostatic image-developing toner as claimed in claim 13,

Wherein by in described oily solution, adding gradually, with described oily solution emulsification or be dispersed in the described aqueous medium to obtain emulsified dispersed liquid through pre-heated aqueous medium and by further interpolation aqueous medium with optionally add surfactant and carry out inversion of phases emulsification.

17. one kind by the prepared electrostatic image-developing toner of electrostatic image-developing toner manufacture method, this method comprises:

But the polycondensation polycondensation monomer to be obtaining the condensation resin particle dispersion in aqueous medium, but wherein said polycondensation monomer contains polybasic carboxylic acid and polyvalent alcohol at least;

Assemble condensation resin particle in the described condensation resin particle dispersion to obtain aggregated particle; With

By heat-setting aggregated particle,

Wherein said condensation resin particle has 0.05 micron～2.0 microns median particle diameter.

18. electrostatic image-developing toner as claimed in claim 17, the cumulative volume mean diameter of wherein said electrostatic image-developing toner are 3.0 microns～5.0 microns.

19. condensation compound particle dispersion that is used to contain the electrostatic image-developing toner of condensation compound particle, but wherein said condensation compound particle prepares by the dehydrating condensation of condensation compound in aqueous medium, and to have be 0.05 micron～2.0 microns median particle diameter, but wherein said condensation compound contains polybasic carboxylic acid and polyvalent alcohol at least, and described condensation compound particle is the ester type waxes particle.

20. condensation compound particle dispersion as claimed in claim 19, wherein said condensation compound particle is a crystal type, and its crystalline melting point is 50 ℃～120 ℃.

21. condensation compound particle dispersion as claimed in claim 19, but wherein said condensation compound carries out dehydration condensation in the presence of as the acid with surfactant properties of dehydrating condensation catalyzer.

22. condensation compound particle dispersion as claimed in claim 19, but wherein said condensation compound carries out dehydration condensation in the presence of as the catalyzer that contains rare earth metal of dehydrating condensation catalyzer.

23. condensation compound particle dispersion as claimed in claim 19, but wherein said condensation compound carries out dehydration condensation in the presence of as the hydrolytic enzyme of dehydrating condensation catalyzer.

24. condensation compound particle dispersion as claimed in claim 19, wherein said median particle diameter are 0.1 micron～1.5 microns.

25. condensation compound particle dispersion as claimed in claim 19, wherein said median particle diameter are 0.1 micron～1.0 microns.

26. condensation compound particle dispersion as claimed in claim 19, wherein with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter is less than or equal to 0.03 micron the weight ratio of condensation compound particle for being less than or equal to 10%, with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter more than or equal to the weight ratio of 5.0 microns condensation compound particle for being less than or equal to 10%.

27. condensation compound particle dispersion as claimed in claim 19, wherein with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter is less than or equal to 0.03 micron the weight ratio of condensation compound particle for being less than or equal to 5%, with respect to the general assembly (TW) of described condensation compound particle, described median particle diameter more than or equal to the weight ratio of 5.0 microns condensation compound particle for being less than or equal to 5%.

28. the manufacture method of an electrostatic image-developing toner, this method comprises:

Dispersion resin is to obtain particulate resin dispersion in aqueous medium;

In aqueous medium, disperse condensation compound to obtain the condensation compound particle dispersion;

Described particulate resin dispersion is mixed to obtain mixed dispersion liquid with described condensation compound particle dispersion, assemble resin particle in the described mixed dispersion liquid and condensation compound particle to obtain aggregated particle; With

By the described aggregated particle of heat-setting,

But wherein said condensation compound particle dispersion prepares by the dehydrating condensation of condensation compound in aqueous medium, and to have be 0.05 micron～2.0 microns median particle diameter, but wherein said condensation compound contains polybasic carboxylic acid and polyvalent alcohol at least, and described condensation compound particle is the ester type waxes particle.

29. the manufacture method of electrostatic image-developing toner as claimed in claim 28, described method also comprises:

In aqueous medium, but described condensation compound is carried out first emulsification or disperse to obtain emulsified dispersed liquid; With

Described emulsified dispersed liquid is carried out second emulsification or disperses to obtain the particulate emulsified dispersed liquid.

30. the manufacture method of electrostatic image-developing toner as claimed in claim 29, wherein at first but condensation compound is mixed with adjuvant and fusion to obtain oily solution, then with described oily solution emulsification and be dispersed in the aqueous medium to obtain emulsified dispersed liquid.

31. the manufacture method of electrostatic image-developing toner as claimed in claim 30, wherein with described oily solution with mix mutually to obtain described emulsified dispersed liquid through pre-heated aqueous medium.

32. the manufacture method of electrostatic image-developing toner as claimed in claim 30, wherein said oily solution with solvent emulsification or be dispersed in aqueous medium with obtain described emulsified dispersed liquid and

Wherein this method also comprises by stirring and heating described particulate emulsified dispersed liquid to remove the solvent in the described particulate emulsified dispersed liquid.

33. the manufacture method of electrostatic image-developing toner as claimed in claim 30,

By in described oily solution, adding gradually, with described oily solution emulsification or be dispersed in the aqueous medium to obtain emulsified dispersed liquid through pre-heated aqueous medium and by further interpolation aqueous medium with optionally add surfactant and carry out inversion of phases emulsification.

34. one kind by the prepared electrostatic image-developing toner of electrostatic image-developing toner manufacture method, this method comprises:

Dispersion resin is to obtain particulate resin dispersion in aqueous medium;

In aqueous medium, disperse condensation compound to obtain the condensation compound particle dispersion;

Described particulate resin dispersion is mixed to obtain mixed dispersion liquid with described condensation compound particle dispersion, assemble resin particle in the described mixed dispersion liquid and condensation compound particle to obtain aggregated particle; With

By the described aggregated particle of heat-setting,

But wherein said condensation compound particle dispersion prepares by the dehydrating condensation of condensation compound in aqueous medium, and to have be 0.05 micron～2.0 microns median particle diameter, but wherein said condensation compound contains polybasic carboxylic acid and polyvalent alcohol at least, and described condensation compound particle is the ester type waxes particle.

35. electrostatic image-developing toner as claimed in claim 34, the cumulative volume mean diameter of wherein said electrostatic image-developing toner are 3.0 microns～5.0 microns.